JP4068679B2 - Polymetal oxide - Google Patents
Polymetal oxide Download PDFInfo
- Publication number
- JP4068679B2 JP4068679B2 JP30644296A JP30644296A JP4068679B2 JP 4068679 B2 JP4068679 B2 JP 4068679B2 JP 30644296 A JP30644296 A JP 30644296A JP 30644296 A JP30644296 A JP 30644296A JP 4068679 B2 JP4068679 B2 JP 4068679B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- acrolein
- acrylic acid
- gas phase
- multimetal oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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- 239000007789 gas Substances 0.000 claims description 67
- 239000000843 powder Substances 0.000 claims description 54
- 238000001228 spectrum Methods 0.000 claims description 53
- 239000003054 catalyst Substances 0.000 claims description 48
- 230000003647 oxidation Effects 0.000 claims description 45
- 238000007254 oxidation reaction Methods 0.000 claims description 45
- 229910044991 metal oxide Inorganic materials 0.000 claims description 40
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 36
- 230000003197 catalytic effect Effects 0.000 claims description 32
- 239000003570 air Substances 0.000 claims description 30
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 28
- 238000010304 firing Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000010949 copper Substances 0.000 claims description 24
- 229910052720 vanadium Inorganic materials 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
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- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 4
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- 229940043376 ammonium acetate Drugs 0.000 claims description 3
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- 239000012080 ambient air Substances 0.000 claims description 2
- IKUPISAYGBGQDT-UHFFFAOYSA-N copper;dioxido(dioxo)molybdenum Chemical compound [Cu+2].[O-][Mo]([O-])(=O)=O IKUPISAYGBGQDT-UHFFFAOYSA-N 0.000 claims description 2
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- 150000004706 metal oxides Chemical class 0.000 claims description 2
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- -1 alkanols Chemical class 0.000 description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000003918 potentiometric titration Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000616 Ferromanganese Inorganic materials 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000010428 baryte Substances 0.000 description 2
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- RXWOHFUULDINMC-UHFFFAOYSA-N 2-(3-nitrothiophen-2-yl)acetic acid Chemical compound OC(=O)CC=1SC=CC=1[N+]([O-])=O RXWOHFUULDINMC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
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- 235000021355 Stearic acid Nutrition 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
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- 239000008246 gaseous mixture Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000007620 mathematical function Methods 0.000 description 1
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- 239000003658 microfiber Substances 0.000 description 1
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
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- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Description
【０００１】
【発明の属する技術分野】
本発明は、一般式Ｉ：
Ｍｏ12-a-b-cＶaＭ1 bＭ2 cＯx （Ｉ）
［式中、
Ｍ1＝Ｗ及び／又はＮｂ、
Ｍ2＝Ｔｉ，Ｚｒ，Ｈｆ，Ｔａ，Ｃｒ，Ｓｉ及び／又はＧｅ、
ａ＝０．１〜６、有利には０．５〜４．５、
ｂ＝０〜６、有利には０．１〜６、特に有利には０．５〜４、
ｃ＝０〜６、しばしば０．１〜６又は０．５〜４、
であり、但しａ＋ｂ＋ｃ＝０．１〜６、有利には０．５〜４．５であり、かつ
ｘ＝式Ｉ中の酸素とは異なる元素の原子価及び頻度により決まる数値
である］の多金属酸化物であって、該多金属酸化物は、その、Ｃｕ-Ｋα放射線（λ＝１．５４１７８Å）を使用して得られた三次元的原子配置が、５〜５０゜の２θ範囲（面内の角度に関する単位で表される）内で少なくとも以下の特性特徴的回折線Ａ1，Ａ3，Ａ5，Ａ9及びＡ10、但し最大でも以下の回折線Ａ1〜Ａ10を含む、Ｘ線粉末回折スペクトル（２倍の回折角度（２θ）の関数としてプロットした回折したＸ線の強度Ａ）：
【０００２】
【表５】
を生じることを特徴とする多金属酸化物に関する。
【０００４】
この場合、回折のために使用されるＸ線の波長λと回折角度θは、互いにブラッグ（Bragg）の関係式：
２ｓｉｎθ＝λ／ｄ
［式中、ｄはそれぞれの回折線に属する、三次元的原子配置の格子面距離である］によって関係付けられる。
【０００５】
更に、本発明は、多金属酸化物Ｉの製造方法並びに該多金属酸化物を有機化合物の接触気相酸化のための活性材料として直接使用することに関する。
【０００６】
本発明はまた、多金属酸化物Ｉを、有機化合物の接触気相酸化のための活性材料として適する、Ｍｏ及びＶを含有する多金属酸化物材料を製造するための出発化合物として使用することに関する。
【０００７】
Ｍｏ及びＶを含有する多金属酸化物材料の製造方法並びに該多金属酸化物材料を有機化合物の接触気相酸化のための活性材料として使用することは公知である（例えば欧州特許出願公開第２９３８５９号明細書参照）。
【０００８】
初期には、このようなＭｏ及びＶを含有する多金属酸化物材料は、その元素成分のそれぞれから適当なソース（出発化合物）を用意し、これらのソースの全量から可能な限り完全な、有利には微細な、所望の多金属酸化物材料の必要とされる化学量論的量に相当して組成された乾燥材料を製造し、この乾燥混合物を高温で数時間不活性ガス又は酸素を含有するガス（例えば空気）下で焼成する（単一容器法）ことにより製造された。この場合、多金属酸化物材料の元素成分ソースのために重要なことは、それらが既に酸化物であるか、又は少なくとも酸素の存在で加熱により酸化物に転化可能である化合物であることである（例えばドイツ国特許出願公開第４３３５９３７号明細書及び米国特許第４,０３５,２６２号明細書参照）。
【０００９】
今や、まず所望の多金属酸化物材料の元素成分の全量の一部を含む多金属酸化物を別に前形成しかつこの別に前形成した一部分の多金属酸化物を引き続き所望の多金属酸化物材料を製造するための微粒子ソースとして使用することが場合により好ましいことも公知である（例えば欧州特許出願公開第８３５号明細書、ドイツ国特許第３３３８３８０号明細書、ドイツ国特許出願公開第４２２０８５９号明細書、ドイツ国特許出願公開第４３０７３８１号明細書、ドイツ国特許出願公開第４４０５０５９号明細書、ドイツ国特許出願公開第４４０５０６０号明細書、ドイツ国特許出願公開第４４０５５１４号明細書及びドイツ国特許出願公開第４４４０９８１号明細書参照）。
【００１０】
この場合には、一般に、自体公知の方法に基づき製造された多金属酸化物材料よりも、有機化合物の接触気相酸化のためにより有利である多相構造を有する多金属酸化物材料が生じる。
【００１１】
【発明が解決しようとする課題】
本発明の課題は、特にアクロレインのアクリル酸への気相接触酸化のための活性材料として好適である、多相のＭｏ及びＶを含有する多金属酸化物材料を製造するための出発化合物として使用可能である、 Ｍｏ及びＶを含有する多金属酸化物材料の新規の部分量金属酸化物を提供することであった。
【００１２】
【課題を解決するための手段】
従って、冒頭に定義した多金属酸化物Ｉが見出された。好ましい多金属酸化物Ｉは、就中ｘ＝１５〜５０を有するものである。有利には、ｘは２５〜４０、特に有利には３０〜４０である。更に、多金属酸化物Ｉの内では、就中ｃ＝０であるのが好適である。ｃ＝０及びＭ1＝専らＷである場合には、バナジウムの≧２５％、又は≧５０％、又は≧７５％、又は≧９５％、又は≧９９％がＶ4+として存在するのが有利である。
【００１３】
新規の多金属酸化物Ｉに関して典型的なことは、そのＣｕ-Ｋα放射線を使用して得られたＸ線粉末回折スペクトルが、５〜５０゜の２θ範囲内で特徴を示す指紋として少なくとも特性回折線Ａ1，Ａ3，Ａ5，Ａ9及びＡ10を含み、但し決して回折線Ａ1，Ａ2， Ａ3， Ａ4，Ａ5，Ａ6，Ａ7，Ａ8，Ａ9及びＡ10より多くを含まないことである。
【００１４】
注目すべきことは、回折線の若干のものが、比較的大きな半値幅ＦＷＨＭ［平面における角度で表される、回折線の最大振幅の半分の高さでの回折線の幅（２θの関数としてプロットした強度）である］を有するものであることであり、このことは新規の多金属酸化物Ｉにおける近配置と遠配置の異常なパターンを反映している（実施例参照）。この近配置と遠配置の特別の形態は、本発明者の見解によれば、就中本発明による多金属酸化物Ｉの特殊な触媒特性に起因すると見なされる。
【００１５】
特殊な半値幅に基づき、本発明による多金属酸化物ＩのＸ線粉末回折スペクトルは、完全に互いに分解されていない形の回折線Ａｉを含む。しかしながら、多数の回折線Ａｉの存在は、（線形バックグラウンドの除去後に）視覚的に直接識別可能な形式で新規の多金属酸化物ＩのＸ線粉末回折スペクトルの外郭線における相対的最大として示され、この相対的最大を本明細書において特許請求の範囲に基づく回折線Ａｉと定義する。
【００１６】
線形バックグラウンド［Ａ（２θ＝５゜とＡ（２θ＝６５゜）との間の結合線］を除いた後、これらの回折線Ａ1〜Ａ10に、更に以下の、回折線Ａ1〜Ａ10の最大強度を基礎とした、相対的線強度（ＩA rel＝（Ｉ／Ｉo）×１００％）を配属させることができ、その際強度尺度として、基線から相対的最大まで測定した振幅を使用する：
【００１７】
【表６】
この線強度データに関しては、相対的線強は、線の位置とは異なり、種々の粉末調製において結晶形の異方性に基づき生じる個々の結晶配向により当業者に周知の形式で顕著に影響される、従って新規の多金属酸化物の同定のためにはあまり重要でないことに留意されるべきである。
【００１９】
この関係において、本出願人の見解によれば、本発明による多金属酸化物ＩのＣｕ-ＫαＸ線粉末回折スペクトルのもう１つの特徴は、一般にＦＷＨＳ＜０．２５゜である回折線を含有しないことに現れることが確認されるべきである。
【００２０】
全ての実施例において、Ｘ線粉末回折スペクトルの記録はジーメンス・ディフラクトメータ（Siemens Diffraktometer)Ｄ-５０００を用いてＣｕ-Ｋα放射線（４０ｋＶ，３０ｍＡ，λ＝１．５４１７８Å）を使用して行った。該ディフラクトメータは、自動一次及び二次コリメータ並びに黒鉛二次モノクロメータを備えていた。
【００２１】
もちろん、多金属酸化物ＩのＸ線粉末回折スペクトルの分解、ひいては選択的特性決定は、線形バックグラウンドを除いた後、最小平均平方偏差の境界条件下で数学的関数によって実験的回折スペクトル（その包絡線）を記述しかつそれを分解して別々に分解した線Ａ1*〜Ａ10*の重ね合わせに展開することにより行うことができる。分解した線の最大は、それぞれそれらの線位置を定義する。
【００２２】
既に述べたＸ線粉末回折スペクトルの数学的分解は、ジーメンス社から調達される１９９４年のバージョンのソフトウエア-パッケージDIFFRAC-AT V 3.2/PROFILEを使用した行った、この場合分解及び適合はペアーソンＶＩＩ形（Pearson-VII-form）関数を基礎として行った。
【００２３】
本発明による多金属酸化物ＩのＣｕ-Ｋα粉末Ｘ線粉末回折スペクトルにあの回折線Ａ2，Ａ4及びＡ6〜Ａ8の、それらの包絡線の専ら視覚的観察を基礎とした存在は部分的にある程度の不確実性と結び付いておりかつひいては場合により議論の余地があるが（実施例参照）、その上記のようにして得られた数学的分解は一般に疑いなく回折線Ａ2*，Ａ4*，Ａ6*及びＡ7*を示す（実施例参照）、それに対して回折線Ａ8*は不必要である。従って、両者の特性決定方法（情報）は一緒に、本発明による対象の特許請求の範囲に記載の定義を必要とする。それに対して、専ら数学的分解によれば、本発明による多金属酸化物ＩのＣｕ-Ｋα粉末Ｘ線粉末回折スペクトルを一般に以下のように特性決定することができる：
【００２４】
【表７】
この場合ＩF rel[％]は、回折線Ａ1*〜Ａ10*の最大強度に対する回折線強度のパーセントであり、その場合強度尺度としては回折線の下の面積を使用する。
【００２６】
本発明による多金属酸化物Ｉは簡単に、その元素成分の適当なソースから、所望の化学量論的量に相当する可能な限り完全な、有利には微粒子の乾燥混合物を製造し、該混合物を３００〜５００℃の範囲内の温度で焼成することにより得られる。その際、本発明による多金属酸化物Ｉを得るためのキーは、高すぎる酸化性でも、また高すぎる還元性でもあってはならない焼成雰囲気のレドックス特性である。
【００２７】
焼成雰囲気の必要なレドックス特性に関する一般的な妥当な定量的データを提供することは不可能である。一面では必要なレドックス特性は選択される化学量論的量で変動し、かつ他面では元素成分の選択されたソースの反対イオン（例えばＮＨ4 +）も焼成中に分解すると、焼成雰囲気のレドックス特性に関与する。しかしながら、調査のための前実験により、当業者は焼成雰囲気の必要なレドックス特性を確認することができる。
【００２８】
その際、焼成雰囲気のレドックス特性を制御するために、当業者は不活性ガスとして例えばＮ2及び／又は希ガスを、還元ガスとして例えばアンモニア、水素、低分子アルデヒド及び／又は炭化水素をかつ酸化ガスとして酸素（大抵は空気の形で）を利用することができる。
【００２９】
元素ソースのために重要なことは単に、それらが既に酸化物であるか、又は少なくとも酸素の介在で、加熱により酸化物に転化可能である化合物であることである。従って、酸化物の他に、出発化合物として就中ハロゲン化物、硝酸塩、ギ酸塩、クエン酸塩、シュウ酸塩、酢酸塩、炭酸塩又は水酸化物が該当する。Ｍｏ，Ｖ，Ｗ及びＮｂの適当な出発化合物はまた、それらのオキソ化合物（モリブデン酸塩、バナジウム酸塩、タングステン酸塩及びニオブ酸塩）であり、該化合物は加熱すると還元作用するＮＨ3を遊離するＮＨ4 +を一般に反対イオンとして有する。もちろん、これらのオキソ化合物から誘導される酸も可能な出発化合物として該当する。更にしばしば、焼成中に気孔形成剤として作用しかつ同様に焼成雰囲気のレドックス特性に影響する化合物、例えば酢酸アンモニウム及び硝酸アンモニウムも添加される。
【００３０】
本発明の範囲内での出発化合物の完全混合は、乾式又は湿式で行うことができる。乾式で行う場合には、出発化合物を好ましくは微細粉末として使用しかつ混合及び場合により圧縮後に、焼成処理する。しかしながら、完全混合は湿式で行うのが有利である。その際には通常、出発化合物を水溶液及び／又は懸濁液の形で相互に混合するのが有利である。引き続き、水性材料を乾燥しかつ乾燥後に焼成する。有利には、乾燥処理は、水性混合物の製造直後にかつ噴霧乾燥により行う（入口温度は一般に２５０〜３５０℃であり、かつ出口温度は一般に１００〜１５０℃である）。
【００３１】
興味深くも、新規の多金属酸化物Ｉは既に、有機化合物の気相接触酸化、例えば３〜６個の炭素原子を有するアルカン、アルカノール、アルケン、アルカナール、アルケナール及びアルケノール（例えばプロピレン、メタクロレイン、ｔ−ブタノール、 ｔ−ブタノールのメチルエステル、イソ−ブタン、イソ−ブテン又はイソ−ブチルアルデヒド）をオレフィン系不飽和アルデヒド及び／又はカルボン酸、並びに相応するニトリルへの気相接触酸化（アンモ酸化、就中プロペンのアクリルニトリルへの及びイソ−ブテンもしくはｔ−ブタノールのメタクリルニトリルへの）のための触媒のための活性材料として好適である。例えば、アクロレイン、メタクロレイン及びメタクリル酸の製造が挙げられる。更に、オレフィン系化合物の酸化性脱水素のための触媒活性材料としても好適である。
【００３２】
この場合、多金属酸化物Ｉは特に疑いなくアクロレインからアクリル酸への気相接触酸化のための触媒の活性材料として好適であり、しかもこの反応に関しては特にその高活性が顕著である。
【００３３】
本発明による多金属酸化物材料を有機化合物の気相接触酸化、特にアクロレインのアクリル酸への気相接触酸化のための触媒の活性材料として使用する際には、所望の触媒形態への成形は有利には前成形した不活性触媒担体に施与することより行う。この場合、該施与は最終的焼成の前又は後に行うことができる。この場合には、常用な担体材料、例えば多孔性又は非多孔性酸化アルミニウム、二酸化珪素、二酸化トリウム、二酸化ジルコニウム、炭化珪素又は珪酸マグネシウムもしくは珪酸アルミニウムのような珪酸塩を使用することができる。担体は規則的に又は非規則的に成形されていてもよく、その際明らかに形成された表面荒さを有する規則的に成形された担体、球又は中空円筒体が有利である。これらの内でもまた球が特に有利である。直径が１〜６ｍｍ、有利には４〜５ｍｍである、ステアタイトからなる実質的に非多孔性の、表面荒さを有する球状担体を使用するのが特に好ましい。活性材料の層厚さは、好ましくは５０〜５００μｍの範囲内、有利には１５０〜２５０μｍの範囲内にあるように選択すべきである。ここで更に言及すれば、このような被覆触媒を製造する際には担体を被覆するために施与すべき粉末材料を一般に湿潤しかつ施与後に例えば熱気を用いて再び乾燥する。
【００３４】
被覆触媒を製造するためには、担体の被覆は一般に適当な回転可能な容器、例えばドイツ国特許出願公開第２９０９６７１号明細書又は欧州特許出願公開第２９３８５９号明細書から公知であるような容器で実施する。一般に、重要な材料は担体被覆前に焼成する。更に、触媒活性材料を被覆を実施する前に０より大であって３００μｍ以下、有利には０．１〜２００μｍ、特に有利には０．５〜５０μｍの範囲内の粒径に粉砕する。好ましくは、被覆工程及び焼成工程は、欧州特許出願公開第２９３８５９号明細書に基づき、生じる多金属酸化物Ｉ層が比表面積０．５０〜１５０ｍ2／ｇ、比気孔容積０．１０〜０．９０ｃｍ3／ｇ、及び気孔容積のそれぞれ少なくとも１０％が直径範囲０．１〜＜１μｍ、１．０〜＜１０μｍ及び１０〜１００μｍに分配されるような気孔直径分布を有するように実施する。欧州特許出願公開第２９３８５９号明細書に有利であるとして挙げられた気孔直径分布に調整することもできる。
【００３５】
もちろん、本発明による多金属酸化物Ｉは、担体無しの触媒として使用することもできる。この場合には、多金属酸化物Ｉの出発化合物からなる完全乾燥混合物を有利には直接所望の触媒形態に圧縮する（例えばペレット加工又は押出成形）。この際には、場合により常用の助剤、例えば黒鉛又はステアリン酸を滑剤及び／又は成形助剤として並びにガラス、アスベスト、炭化珪素又はチタン酸カリウムからなるマイクロ繊維のような強化剤を加えることができる。前記圧縮に引き続き焼成する。この場合も、一般に成形前に焼成することもできる。
【００３６】
有利な担体無しの触媒形態は、外径及び長さ２〜１０ｍｍ並びに壁厚さ１〜３ｍｍを有する中空円筒体である。
【００３７】
触媒活性材料として新規の多金属酸化物Ｉを用いてアクロレインをアクリル酸に接触気相酸化するためには、一般に、プロペンの接触気相酸化により製造したアクロレインを使用する。一般に、このプロペン酸化から得られた中間精製していないアクロレインを含有する反応ガスをを使用する。通常、アクロレインの気相接触酸化は、管束式反応器内で不均一固床酸化として実施する。酸化剤としては、自体公知の形式で酸素を、有利には不活性ガスで希釈して（例えば空気の形で）使用する。適当な希釈剤は、例えばＮ2，ＣＯ2、炭化水素、例えばメタン、エタン、プロパン、ブタン及び／又はペンタン、再循環した反応ガス及び／又は水蒸気である。一般に、アクロレイン酸化の際にはアクロレイン：酸素：水蒸気：不活性ガスの容量比は１：（１〜３）：（０〜２０）：（３〜３０）、有利には１：（１〜３）：（０．５〜１０）：（７〜１８）に調整する。反応圧は、一般に１〜３バールでありかつ全空間速度は、有利には１０００〜３５００Ｎｌ／ｌ／ｈである。典型的な多管式固床反応器は、例えば刊行物ドイツ国特許出願公開第２８３０７６５号明細書、ドイツ国特許出願公開第２２０１５２８号明細書又は米国特許第３,１４７,０８４号明細書に記載されている。反応温度は通常、アクロレイン転化率が１回の通過で９０％以上、有利には９８％以上であるように選択する。通常、このためには２３０〜３３０℃の反応温度が必要である。
【００３８】
注目すべきことに、本発明による多金属酸化物Ｉはアクロレインからアクリル酸への接触気相酸化において、高い活性だけでなく、驚異的に短い成形時間を有する、即ち本発明による多金属酸化物Ｉを装填した管束式反応器を所定の条件下でアクロレインを含有するガス流を用いてアクリル酸の酸化形成のために運転した場合、アクリル酸形成の選択率は既に短い運転時間内でそのプラトー値に達する。このプラトー値に関して、本発明による多金属酸化物材料の製造は高い再現性を有する。
【００３９】
しかしながら、多金属酸化物Ｉは、前記の利点を維持した上での、有機化合物、特にアクロレインのアクリル酸への接触気相酸化のための触媒活性材料としての能力は、次の場合初めて完全に発揮される。即ち、前記能力は、前記多金属酸化物Ｉを、一般式ＩＩ：
Ｍ3 12ＣｕdＨeＯy （ＩＩ）
［式中、
Ｍ3＝Ｍｏ，Ｗ，Ｖ，Ｎｂ及び／又はＴａ、
ｄ＝４〜３０、有利には６〜２４、特に有利には９〜１７、
ｅ＝０〜２０、有利には０〜１０及び
ｙ＝式ＩＩ中の酸素とは異なる元素の原子価及び頻度により決まる数値
である］の微細多金属酸化物で希釈し、そうして一般式III：
［Ａ］p［Ｂ］q （III）
［式中、
【００４０】
【数３】
Ｂ＝Ｍ3 12ＣｕdＨeＯy （プロモータ相）、
ｐ，ｑ＝０とは異なる数値、その比ｐ／ｑは１６０：１〜１：１、有利には２０：１〜１：１、特に有利には１５：１〜４：１である］を有し、
成分［Ａ］pを三次元的に拡がり、その局所的周囲からその局所的周囲とは異なる化学的組成に基づき境界付けられる化学組成：
Ａ Ｍｏ12-a-b-cＶaＭ1 bＭ2 cＯx
の領域Ａの形で、かつ
成分［Ｂ］qを三次元的に拡がり、その局所的周囲からその局所的周囲とは異なる化学的組成に基づき境界付けられる化学組成：
Ｂ Ｍ3 12ＣｕdＨeＯy
の領域Ｂの形で含有し、その際、領域Ａ，Ｂは互いに相対的に微粒子状Ａと微粒子状Ｂからなる混合物におけように分配されている、少なくとも２相の多金属酸化物材料を製造する際に達成される。
【００４２】
このような多金属酸化物材料IIIを製造するためには、特に簡単には、多金属酸化物Ｉ及びＩＩを予め別々に製造し、次いで少なくとも１種の微細な、別々に前製造した多金属酸化物Ｉ及び少なくとも１種の微細な、別々に前製造した多金属酸化物ＩＩを所望の混合比で完全乾燥混合物を製造し（この場合、完全混合は湿式又は乾式で行うことができる；湿式、一般には水性で行う場合には、引き続いて乾燥する；該混合はニーダー又はミキサーで行うことができる）、次いで該完全乾燥混合物から、多金属酸化物Ｉに関してのみ記載したと同じ方法で成形により有機化合物の接触気相酸化、特にアクロレインのアクリル酸への接触気相酸化のために好適な触媒を製造することができる。しかしもちろん、多金属酸化物Ｉもまた多金属酸化物IIIも粉末の形で触媒として使用することができる。同様にもちろん、多金属酸化物材料IIIを、多金属酸化物Ｉも適用であると記載した全ての接触気相酸化のために使用することができる。活性材料として多金属酸化物材料IIIをベースとする触媒をアクロレインからアクリル酸への接触気相酸化のために使用する場合には、該酸化は一般に多金属酸化物Ｉ触媒の相応する単独の使用のために記載したと同じ操作条件下で行う。
【００４３】
多金属酸化物ＩＩは、当業者に周知の簡単な方法で以下のようにして製造することができる。多金属酸化物ＩＩの元素成分の適当なソースから可能な限り完全な、有利には微細な乾燥混合物を製造し、該混合物を２００〜１０００℃、しばしば２５０〜６００℃、大抵は３００〜５００℃の温度で焼成する。その際、焼成は、例えばドイツ国特許出願公開第４３３５９７３号明細書に記載されているように、不活性ガス（例えばＮ2）、不活性ガスと酸素の混合物（例えば空気）、還元作用ガス、例えば炭化水素（例えばメタン）、アルデヒド（例えばアクロレイン）又はアンモニア、更にまたＯ2と還元作用ガス（例えば前記の全てのもの）の混合物下で実施することができる。注目すべきことにも、この場合も焼成雰囲気は水蒸気を含有していてもよい。還元条件下で焼成を実施する場合には、金属成分が元素まで還元されないように注意すべきである。焼成温度が高くなるほど、一般に焼成時間は短くなる。
【００４４】
多金属酸化物ＩＩのソースに関しては、実質的に多金属酸化物Ｉの元素成分のソースに関すると同じことが当てはまる。この場合も重要なことは、該ソースが既に酸化物であるか、又は少なくとも酸素の存在下で、加熱により酸化物に転化可能である化合物であることのみである。多金属酸化物ＩＩの有利な製造変更法では、使用出発化合物の完全混合物をオートクレーブ中で過圧を有する水蒸気の存在下に１００より高く６００℃以下の温度で行う。
【００４５】
その都度選択した焼成条件に基づき、生成する多金属酸化物ＩＩは種々の三次元的原子配置を有する。特に、本発明のためには、ドイツ国特許出願公開第４４０５５１４号明細書及びドイツ国特許出願公開第１９５２８６４６号明細書に可能な基本的相もしくはプロモータ相として記載された全ての多金属酸化物ＩＩが該当する。即ち、好ましい多金属酸化物ＩＩは、就中、以下の表に列記したモリブデン酸銅の少なくとも１つの構造型（Ｘ線回折パターン）を有するものである（括弧内の表示は、所属のＸ線回折指紋のためのソースを表す）：
【００４６】
【表８】
アクロレインからアクリル酸への接触気相酸化のために特に適当な多金属酸化物材料IIIを製造するために推奨される多金属酸化物ＩＩとしては、一般式ＩＶ：
ＣｕＭｏAＷBＶCＮｂDＴａEＯY・（Ｈ2Ｏ）F （ＩＶ）
［式中、
１／（Ａ＋Ｂ＋Ｃ＋Ｄ＋Ｅ）＝０．７〜１．３、
Ｆ ＝０〜１、
Ｂ＋Ｃ＋Ｄ＋Ｅ ＝０〜１及び
Ｙ＝式ＩＶ中の酸素とは異なる元素の原子価及び頻度により決まる数値
である］で示され、かつその三次元的原子配置が、Russian Jounal of Chmistry 36 (7) (1991), 921, 表１に定義されかつドイツ国特許出願公開第４４０５５１４号明細書並びにドイツ国特許出願公開第４４４０８９１号明細書にヴォルフラミット（Wolfamit）として記載されたものが挙げられる。
【００４８】
多金属酸化物ＩＶのうちではまた、化学量論的式Ｖ：
ＣｕＭｏAＷBＶCＯY （Ｖ）
［式中、
１／（Ａ＋Ｂ＋Ｃ）＝０．７〜１．３、
Ａ，Ｂ，Ｃ ＝全て０より大、但しＢ＋Ｃ≦１、
Ｙ＝式Ｖ中の酸素とは異なる元素の原子価及び頻度により決まる数値
である］で示されるもの、並びに化学量論的式ＶＩ：
ＣｕＭｏAＷBＯY （ＶＩ）
［式中、
１／（Ａ＋Ｂ ）＝０．７〜１．３、
Ａ／Ｂ，Ｃ ＝０．０１〜１０、有利には０．０１〜１及び
Ｙ＝式ＶＩ中の酸素とは異なる元素の原子価及び頻度により決まる数値
である］で示されるものが注目すべきである。多金属酸化物ＩＶ，Ｖ及びＶＩの製造方法は、ドイツ国特許出願公開第４４０５５１４号明細書及びドイツ国特許出願公開第４４４０８９１号明細書に示されている。
【００４９】
更に特に好適である多金属酸化物ＩＩとしては、一般式ＶＩＩ：
ＣｕＭｏA ′ＷB ′ＶC ′ＮｂD ′ＴａE ′ＯY ′ （ＶＩＩ）
［式中、
１／（Ａ′＋Ｂ′＋Ｃ′＋Ｄ′＋Ｅ′）＝０．７〜１．３、有利には０．８５〜１．１５、特に有利には０．９５〜１．０５、全く特に有利には１、
（Ｂ′＋Ｃ′＋Ｄ′＋Ｅ′）／Ａ′ ＝０．０１〜１０、有利には０．０５〜３、特に有利には０．０７５〜１．５及び
Ｙ′＝式ＶＩＩ中の酸素とは異なる元素の原子価及び頻度により決まる数値
である］で示され、かつその構造型がドイツ国特許出願公開第１９５２８６４６号明細書に記載されたＨＴ−Ｃｕモリブデン酸塩型のものである。
【００５０】
この場合、多金属酸化物ＶＩＩのうちでは、 Ｃ′＋Ｄ′＋Ｅ′＝０であるものも有利である。多金属酸化物ＩＩとして特に推奨されるＶＩＩは、組成：
Ｍｏ10.8Ｗ1.2Ｃｕ12Ｏ42-48
を有するものである。
【００５１】
更に、可能な多金属酸化物ＩＩとしては、ドイツ国特許出願公開第１９５２８６４６号明細書に開示されているような多金属酸化物ＩＶとＶＩＩの混合物が挙げられる。このことは、特に多金属酸化物ＩＶとＶＩＩを連晶した形で含有するものに対して当てはまる。
【００５２】
もちろん、別々に前製造した微細な多金属酸化物ＩとＩＩから製造した混合物をその使用前に多金属酸化物III触媒を製造するためにまず圧縮し、次いで粉砕し、かつその後初めて所望の触媒形に加工することもできる。この場合には、最大粒子直径のためには、別々に前製造した多金属酸化物Ｉ及びＩＩの場合と同様に、０より大で３００μｍ以下、特に有利には０．５〜５０μｍ、全く特に有利には１〜３０μｍの直径範囲が推奨される。
【００５３】
本発明による多相多金属酸化物材料III触媒の特別の利点は、種々の相を得るために必要な焼成条件が一般に互いに異なっていることにある。別々の前製造の原理により、焼成条件をそれぞれ所望の相に最適に合わせることができる。
【００５４】
多金属酸化物Ｉは、前記の用途を越えて全く一般的に、例えばドイツ国特許出願公開第４３３５９７３号明細書、米国特許第４,０３５,２６２号明細書、ドイツ国特許出願公開第４４０５０５８号明細書、ドイツ国特許出願公開第４４０５０５９号明細書、ドイツ国特許出願公開第４４０５０６０号明細書、ドイツ国特許出願公開第４４０５５１４号明細書、ドイツ国特許出願公開第４４４０８９１号明細書及びドイツ国特許出願公開第１９５２８６４６号明細書に記載された触媒活性多金属酸化物材料の性能を改良するために好適である。
【００５５】
この目的のためには簡単に、前記刊行物に記載の活性材料を微細な形で微細な多金属酸化物Ｉと混合しかつ多金属酸化物材料III触媒を製造するための完全出発混合物と同様に成形する。
【００５６】
特に、多金属酸化物Ｉは、、ドイツ国特許出願公開第４４０５０５８号明細書、ドイツ国特許出願公開第４４０５０５９号明細書、ドイツ国特許出願公開第４４０５０６０号明細書、ドイツ国特許出願公開第４４０５５１４号明細書及びドイツ国特許出願公開第４４４０８９１号明細書に開示された多相多金属酸化物材料触媒の共相の成分として好適である。更に、多金属酸化物Ｉは、ドイツ国特許出願公開第１９５２８６４６号明細書に記載された多相多金属酸化物材料触媒の活性相の成分として好適である。これらの全ての場合、微細な（０より大で３００μｍ以下）の均一な分布の多金属酸化物Ｉからなる相を含有する多相の多金属酸化物材料触媒が生成する。これらは特に前記に引用したそれぞれの文献に記載された有機化合物の接触気相酸化ための触媒として好適である。
【００５７】
最後に、本発明により初めて純粋な多金属酸化物Ｉの製造が可能になったことに注目されるべきである。
【００５８】
【実施例】
１）本発明による多金属酸化物ＭＩ１〜ＭＩ９及び比較多金属酸化物ＶＭＩ１及びＶＭＩ２の製造及び同定
一般的説明
以下に記載の本発明による多金属酸化物Ｉは元素成分Ｍｏ及びＷを常に酸化状態＋６で含有する。これに対して元素成分Ｖの酸化状態は一般にこの可能な酸化状態Ｖ3+、Ｖ4+及びＶ5+における分布である。この分布の測定は電位差滴定による最終点表示を用いた容量分析（組み合わせた白金電極及びポテンシオグラフ、Ｍｅｔｒｏｈｍ、９１００ Ｈｅｒｉｓａｕ、スイス）により可能であり、その際不活性ガス雰囲気下で処理しなければならなかった。８０℃で滴定を実施することにより最終点の検出が容易になった。そのほか、電位差滴定の容量分析はすべての場合に以下の通り実施した。
【００５９】
酸化物試料物質それぞれ０.１５ｇを加熱下で、濃縮した燐酸５ｍｌ（２０℃の密度ρ＝１.７０ｇ／ｃｍ3）及び水性硫酸１０ｍｌからなる混合物に溶かし（アルゴン雰囲気）、その際使用した硫酸水溶液は同じ量の水及び濃縮した硫酸（ρ20＝１.５２ｇ／ｃｍ3）からなる混合物であった（容量表示は２０℃に関する）。Ｖの可能な酸化状態が変動しないように溶剤を選択し、これを相当するＶ標準規格により検査した。
【００６０】
Ｖ5+含量を分析するために、新たに製造し、生じた溶液を０.１モルの硫酸鉄アンモニウム標準水溶液（（ＮＨ4）2Ｆｅ（ＳＯ4）2）で滴定した。Ｖ3+及びＶ4+を分析するために、適当な方法で製造した新しい溶液を新たに製造した０.０２モルの過マンガン酸カリウム標準水溶液（ＫＭｎＯ4）で滴定し、その際２つの電位の飛躍が生じた（Ｖ3+→Ｖ4+及びＶ4+→Ｖ5+）。前記のように測定したＶ3+含量、Ｖ4+含量及びＶ5+含量の合計は試料のＶ全含量に相当しなければならない。これは同様に電位差滴定の最終点表示を用いた容量分析により測定できた。
【００６１】
そのために、酸化物試料物質０.１５ｇを、加熱下で、前記の半濃縮した硫酸水溶液１０ｍｌ及び濃縮した硝酸１０ｍｌ（ρ20＝１.５２ｇ／ｃｍ3）からなる混合物に溶かした（アルゴン雰囲気）。引き続き得られた溶液を加熱することにより硝酸及び使用した硫酸の一部を蒸発して残留容量約３ｍｌに濃縮し、その際全部のＶ成分が酸化状態＋５に移行した。冷却後残留容量を５０ｍｌに希釈し、存在するＶ5+を０.１モルの（ＮＨ4）2Ｆｅ（ＳＯ4）2標準水溶液で当量点（最終点）をこえて更に電位差滴定した。
【００６２】
こうして得られた水溶液を新たに製造した０.０２モル過マンガン酸カリウム標準水溶液で滴定し、その際２つの電位の飛躍が生じた。最初の電位の飛躍は使用した過剰のＦｅ2+を生じ、第２の電位の飛躍はＶ4+からＶ5+に酸化するために必要な量のＫＭｎＯ4を供給し、これは試料のＶ全含量に相当する。
【００６３】
ＭＩ１：Ｍｏ8.54Ｖ2.47Ｗ0.95Ｏ33.53
ヘプタモリブデン酸アンモニウム水和物３３.７４６ｋｇ（ＭｏＯ3含量：８１.８重量％、理想組成：（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ）、メタバナジン酸アンモニウム６.５７６ｋｇ（Ｖ2Ｏ5含量：７６.５重量％、理想組成：ＮＨ4ＶＯ3）、パラタングステン酸アンモニウム水和物５.７６４ｋｇ（ＷＯ3含量：８９.０重量％、理想組成：（ＮＨ4）10Ｗ12Ｏ41・７Ｈ2Ｏ）及び酢酸アンモニウム７.０３３ｋｇ（ＣＨ3ＣＯＯＮＨ4含量：９７.０重量％、理想組成： ＣＨ3ＣＯＯＮＨ4）を９０℃の温度で、前記の順序で、順次水２５０ｌに撹拌して溶かした。生じた黄色からオレンジ色の溶液を８０℃に冷却し、入口温度３００℃及び出口温度１１０℃で噴霧乾燥した。
【００６４】
得られた噴霧粉末８００ｇを、有効容量２.５ｌを有する混練機（形式：ＬＵＫ２.５、Ｗｅｒｎｅｒ ｕｎｄ Ｐｆｌｅｉｄｅｒｅｒ、７０００ Ｓｔｕｔｔｇａｒｔ、ドイツ）中で、水２５０ｇを添加して１時間混練した。その際水２５０ｇのうち１８０ｇを最初の１０分以内で混練物に及び７０ｇを残りの５０分以内で混練物に添加した。生じた湿った塊状の混練生成物を１１０℃の温度で１５時間乾燥し、その後メッシュ幅５ｍｍのふるいにより圧縮した。
【００６５】
引き続き、その際生じたグラニュール１００ｇを、等温に加熱した石英球容量１ｌを有する水平の回転炉中で、回転速度１２rpmで焼成した。その際以下のように焼成条件を形成した。
【００６６】
第１段階：装入したグラニュールを５０分以内で連続的に２５℃から２７５℃に加熱する、
第２段階：装入したグラニュールを３０分以内で連続的に２７５℃から３２５℃に加熱する、
第３段階：装入したグラニュールを３２５℃で４時間保持する、
第４段階：装入したグラニュールを３０分以内で連続的に３２５℃から４００℃に加熱する、
第５段階：装入したグラニュールを４００℃で１０分保持する。
【００６７】
引き続き、回転炉の外部加熱を中断し、周囲空気を外部から吹き付けることにより炉を冷却した。その際装入したグラニュールは５時間以内で２５℃に冷却した。
【００６８】
個々の焼成段階の間に、回転炉の内部空間に、回転軸に平行に、以下の組成を有するガス混合物を貫流させた（標準温度及び圧力条件（Ｎ）＝１気圧、２５℃）。
【００６９】
第１段階、第２段階及び第３段階：
空気３.６Ｎｌ／ｈ、ＮＨ3１.５Ｎｌ／ｈ及びＮ２４４.９Ｎｌ／ｈ
（全ガス流量：５０Ｎｌ／ｈ）。
【００７０】
第４段階、第５段階及び冷却段階：
空気３.６Ｎｌ／ｈ及びＮ２４４.９Ｎｌ／ｈ
（全ガス流量：４８.５Ｎｌ／ｈ）。
【００７１】
生じた粉末状の多金属酸化物ＭＩ１は黒い色及び比表面積１５.０ｍ2／ｇ（ＤＩＮ６６１３１により、Ｂｒｕｎａｕｅｒ−Ｅｍｍｅｔ−Ｔｅｌｌｅｒ（ＢＥＴ）によるガス吸着（Ｎ2）により決定した）を有した。多金属酸化物ＭＩ１に含まれるバナジウムはＶ4+として９９％より多く存在した（前記のように測定した）。従って多金属酸化物ＭＩ１はＭｏ8.54Ｖ2.47Ｗ0.99Ｏ33.53の化学量論を有した。
【００７２】
実施例により測定した及び線形のバックグラウンドを除去した後に評価されるＣｕ−Ｋα粉末Ｘ線回折スペクトルは重要な２θ範囲（５゜〜５０゜）で以下の回折線を有した。
【００７３】
【表９】
【表１０】
多金属酸化物ＭＩ１の原子の空間配置を反映する実験により測定したＣｕ−Ｋα粉末Ｘ線回折スペクトルを図１に示す（縦軸：強度、絶対数値として示される、横軸：２θ範囲５゜〜６５゜）。
【００７６】
更に図１は評価の枠内で減衰すべき線形のバックグラウンド（Ａ（２θ＝５゜）とＡ（２θ＝６５゜）の結線）及び個々の回折曲線Ａｉの位置を示す。基準線とＸ線回折スペクトルの接点は回折スペクトルを自然な方法で２つの２θ範囲５゜〜４３゜及び４３゜〜６５゜に配分する。
【００７７】
図２は多金属酸化物ＭＩ１のＣｕ−Ｋα粉末Ｘ線回折スペクトルの２θ範囲５゜〜４３゜の拡大図である。更に図２は（バックグラウンド線を含めて）この範囲で実施した数学的適合及び解像の結果を示す（ＰＲＯＦＩＬＥ、Ｐｅａｒｓｏｎ−ＶＩＩプロフィル関数、固定したバックグラウンド）。数学的に形成された回折線Ａｉ *の重なりは実験による輪郭線に適合する。
【００７８】
図３は相当する方法で拡大した２θ範囲４３゜〜６５゜及び線形のバックグラウンド線を含めたこの範囲で実施した解像を示す。
【００７９】
図２及び図３の本来のＸ線回折スペクトルの上に見られる長方形の断面は、それぞれ粉末Ｘ線回折スペクトルの実験による輪郭線とその数学的適合の差の線を示す。この差は良好な適合の尺度である。
【００８０】
ＭＩ２：Ｍｏ8.54Ｖ2.47Ｗ0.99Ｏ33.53
ＭＩ１と同様にグラニュールを製造した。グラニュール４００ｇをジェット反応器の原理により作動する焼成炉中で焼成した。その際装入したグラニュールは金網上で堆積高さ５ｃｍで存在し、これに下からガス混合物を貫流した。炉の容量は３ｌであり、循環比（循環するガス混合物容量流と新たに供給されるガス混合物容量流の比）を２０に選択した。装入したグラニュールを前記の炉中でまず１時間以内で連続的に２５℃から３２５℃に加熱した。引き続き、装入したグラニュールを３２５℃で４時間保持した。焼成の開始時に、貫流するガス混合物はＮ2１２０Ｎｌ／ｈ、空気１０Ｎｌ／ｈ及びＮＨ3３.３Ｎｌ／ｈからなる組成を有した。引き続き、装入したグラニュールを２０分以内で３２５℃から４００℃に加熱し、その後なお１時間４００℃に保持した。この最終段階でＮ2１２０Ｎｌ／ｈ及び空気１０Ｎｌ／ｈからなるガス混合物を貫流した。熱供給を中断することにより、室温に冷却した。
【００８１】
粉末状の多金属酸化物ＭＩ２が得られ、これはＶ5+分析、Ｖ4+分析、Ｖ3+分析に関して及びＣｕ−Ｋα粉末のＸ線回折スペクトルに関して多金属酸化物ＭＩ１と同じであった。
【００８２】
ＭＩ３：Ｍｏ8.35Ｖ2.60Ｗ1.05Ｏ33.40
ヘプタモリブデン酸アンモニウム水和物８５２.７８ｇ（ＭｏＯ3含量：８１.０重量％、理想組成：（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ）、メタバナジン酸アンモニウム１７７.１４ｇ（Ｖ2Ｏ5含量：７７.０重量％、理想組成：ＮＨ4ＶＯ3）及びパラタングステン酸アンモニウム水和物１５６.２９ｇ（ＷＯ3含量：８９.０重量％、理想組成：（ＮＨ4）10Ｗ12Ｏ41・７Ｈ2Ｏ）を、９５℃の温度で前記の順序で、順次水５ｌに溶かした。得られた黄色からオレンジ色の溶液を８０℃に冷却し、入口温度３００℃及び出口温度１１０℃で噴霧乾燥した。引き続き噴霧乾燥した粉末１００ｇを、等温加熱した石英球容量１ｌを有する水平の回転炉中で、回転速度１２rpmで、以下に定義された条件下で焼成した。第１段階で、装入した粉末を５０分以内で連続的に２５℃から２７５℃に加熱し、第１段階に直接続く第２段階で、装入した粉末を３０分以内で連続的に２７５℃から３２５℃に加熱し、第２段階に直接続く第３段階で、装入した粉末を３２５℃で４時間保持し、第３段階に直接続く第４段階で、装入した粉末を３.５時間以内で３２５℃から４００℃に加熱した。最初の３つの段階の間に、石英球に、空気９．６Ｎｌ／ｈ、ＮＨ３３Ｎｌ／ｈ及びＮ２８７.４Ｎｌ／ｈからなるガス混合物（全ガス流量：１００Ｎｌ／ｈ）を貫流した。第４段階の間に、石英球に、空気９.６Ｎｌ／ｈ及びＮ2８７.４Ｎｌからなるガス混合物（全ガス流量：９７Ｎｌ／ｈ）を貫流した。第４段階終了後、回転炉の外部加熱を中断し、外部から空気を吹き付けることにより冷却した。その際装入した粉末を、変化せずに石英球を貫流する、空気９.６Ｎｌ／ｈ及びＮ2８７.４Ｎｌ／ｈからなるガス混合物下で５時間以内で２５℃に冷却した。
【００８３】
生じた粉末状の多金属酸化物ＭＩ３は黒い色及び比表面積０.５ｍ2／ｇ（ＤＩＮ６６１３１）を有した。多金属酸化物ＭＩ３に含まれるバナジウムはＶ4+として９９％より多く存在した。従って多金属酸化物ＭＩ３は、Ｍｏ8.35Ｖ2.60Ｗ1.05Ｏ33.40の化学量論を有した。
【００８４】
所属のＣｕ−Ｋα粉末Ｘ線回折スペクトルを図４〜図６に示す。ＭＩ１と共通の原子の空間配置を示す。ＭＩ１と同様に実施した評価により重要な２θ範囲で以下の回折線が生じた。
【００８５】
【表１１】
【表１２】
ＭＩ４：Ｍｏ8.35Ｖ2.60Ｗ1.05Ｏ33.40
ＭＩ３と同様に噴霧乾燥した粉末を製造した。引き続き、噴霧乾燥した粉末６０ｇを、等温加熱した石英球容量１ｌを有する水平の回転炉中で、回転速度１２rpmで、以下に定義した条件下で焼成した。第１段階で、装入した粉末を５０分以内で２５℃から２７５℃に加熱し、第１段階に直接続く第２段階で、装入した粉末を３０分以内で連続的に２７５℃から３２５℃に加熱し、第２段階に直接続く第３段階で、装入した粉末を３２５℃で３時間保持し、第３段階に直接続く第４段階で、装入した粉末を９０分以内で３２５℃から４００℃に加熱し、１０分後に引き続き４００℃に保持した。最初の３つの段階の間に、石英球に、空気４.８Ｎｌ／ｈ、ＮＨ3１.５Ｎｌ／ｈ及びＮ2４３.７Ｎｌ／ｈからなるガス混合物（全ガス流量：５０Ｎｌ／ｈ）を貫流した。第４及び第５段階の間に、石英球に、空気４.８Ｎｌ／ｈ及びＮ2４３.７（標準）ｌ／ｈからなるガス混合物（全ガス流量：４８.５Ｎｌ／ｈ）を貫流した。第５段階終了後、回転炉の外部加熱を中断し、外部から空気を吹き付けることにより冷却した。その際装入した粉末は、変化せずに石英球を貫流する、空気４.８Ｎｌ／ｈ及びＮ2４３.７Ｎｌ／ｈからなるガス混合物下で５時間以内で２５℃に冷却した。
【００８８】
粉末状の多金属酸化物ＭＩ４が得られ、これはＶ5+分析、Ｖ4+分析、Ｖ3+分析に関して及びＣｕ−Ｋα粉末Ｘ線回折スペクトルに関して多金属酸化物ＭＩ３と同じであった。前記のように実施したＸ線回折スペクトル（図７〜図９に示される）の定量的評価により重要な２θ範囲で以下の回折線が生じた。
【００８９】
【表１３】
【表１４】
ＭＩ５：Ｍｏ8.54Ｖ2.47Ｗ0.99Ｏ33.01
ＭＩ１を製造するために形成された噴霧粉末８００ｇを、有効容量２.５ｌを有する混練機（形式：ＬＵＫ２.５、Ｗｅｒｎｅｒ ｕｎｄ Ｐｆｌｅｉｄｅｒｅｒ、７０００ Ｓｔｕｔｔｇａｒｔ、ドイツ）中で、酢酸８０ｇ（１００％）及び水２００ｇを添加して１時間混練した。その際最初の１０分間に酢酸８０ｇ及び水８０ｇを混練物に添加した。残りの５０分間に残りの水１２０ｇを混練物に添加した。生じた湿った塊状の混練生成物を１１０℃の温度で１５時間乾燥し、その後メッシュ幅５ｍｍのふるいにより圧縮した。その際生じたグラニュール１００ｇを引き続き水平の回転炉中でＭＩ１に記載と同様に焼成した。
【００９２】
生じた粉末状の多金属酸化物ＭＩ５は黒い色及び比表面積１６.０ｍ2／ｇ（ＤＩＮ６６１３１）を有した。多金属酸化物ＭＩ５に含まれるバナジウムはＶ3+として４２％及びＶ4+として５８％の割合で存在した。従って多金属酸化物ＭＩ５は多金属酸化物ＭＩ１と異なり、Ｍｏ8.54Ｖ2.47Ｗ0.99Ｏ33.01の化学量論を有した。それにもかかわらず、多金属酸化物ＭＩ１と同様に測定し、評価したＣｕ−Ｋα粉末Ｘ線回折スペクトルは多金属酸化物ＭＩ５に関して多金属酸化物ＭＩ１と同じ原子の空間配置を反映した（図１０〜１２参照）。測定した回折線は重要な２θ範囲（５゜〜５０゜）で以下の通りである。
【００９３】
【表１５】
【表１６】
ＶＭＩ１：Ｍｏ8.54Ｖ2.47Ｗ0.99Ｏ34.18
ＭＩ５を製造するために、噴霧粉末を水及び酢酸と混練することにより得られたグラニュール１００ｇを、例ＭＩ１に記載されたように水平の回転炉中で焼成した。ただし種々のガス混合物の代わりにそれぞれ相当する量の純粋な空気が回転炉を貫流した。
【００９６】
生じた粉末状の多金属酸化物ＶＭＩ１は黒い色及び比表面積１６.２ｍ2／ｇ（ＤＩＮ６６１３１）を有した。多金属酸化物ＶＭＩ１に含まれるバナジウムはＶ４ +として４７％及びＶ５ +として５３％の割合で存在した。従って多金属酸化物ＶＭＩ１は多金属酸化物ＭＩ１及びＭＩ５と異なり、Ｍｏ8.54Ｖ2.47Ｗ0.99Ｏ34.18の化学量論を有した。所属のＣｕ−Ｋα粉末Ｘ線回折スペクトルを図１３に示す。これは明らかに多金属酸化物ＭＩ１のスペクトルと異なり、２θ範囲５゜〜５０゜で、たとえば以下の（かなり低い半値幅を有する）強い回折線を有する。
【００９７】
【表１７】
すなわち、多金属酸化物ＶＭＩ１の原子の空間配置は多金属酸化物ＭＩ１又はＭＩ５の配置に相当しない。
【００９９】
ＭＩ６：Ｍｏ9.6Ｖ2.4Ｏ34.37
８０℃で、第１の容器中でシュウ酸二水和物２３９.７４ｇ（理想組成：Ｈ2Ｃ2Ｏ4・２Ｈ2Ｏ,Ｈ2Ｃ2Ｏ4含量：７１.４重量％）を水４ｌに溶かした。引き続き生じた水溶液中で８０℃に維持してポリバナジン酸アンモニウム９０.２２ｇ（Ｖ2Ｏ5含量：８８.２重量％、理想組成：（ＮＨ4）2Ｖ6Ｏ16）を撹拌して溶かし、その際濃い青色の水溶液Ａが生じた。その際、反応バッチの泡立ちを回避するために、ポリバナジン酸アンモニウムを１５分以内で少量ずつ添加した。第２の容器中でヘプタモリブデン酸アンモニウム水和物６１９.６０ｇ（ＭｏＯ3含量：８１.３重量％、理想組成：（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ）を８０℃の温水４ｌに撹拌して溶かした（溶液Ｂ）。引き続き８０℃で溶液Ｂを１５分以内で連続的に溶液Ａに撹拌して入れた。その際生じた濃い青色の水溶液を８０℃でなお１５時間後撹拌し、引き続き噴霧乾燥した（入口温度：３１０℃、出口温度：１１０℃）。
【０１００】
噴霧乾燥した粉末１００ｇを、等温加熱した石英球容量１ｌを有する水平の回転炉中で、回転速度１２rpmで、以下の条件下で焼成した。第１段階で、装入した粉末を５０分以内で連続的に２５℃から２７５℃に加熱し、第１段階に直接続く第２段階で、装入した粉末を３５分以内で連続的に２７５℃から３２５℃に加熱し、これに直接続く第３段階で、３２５℃で４時間保持した。その後直ちに装入した粉末を第４段階で３５分以内で３２５℃から４００℃に加熱し、直接続く第５段階で４００℃で１０分間保持した。引き続き回転炉の外部加熱を中断し、空気を外部から吹き付けることにより石英球を冷却した。その際装入した粉末は５時間以内で室温（２５℃）に冷却した。（冷却段階を含めて）全焼成時間の間、石英球に５０Ｎｌの空気流を貫流した。
【０１０１】
生じた粉末状の多金属酸化物ＭＩ６は黒い色及び比表面積６.６ｍ2／ｇ（ＤＩＮ６６１３１）を有した。多金属酸化物ＶＭＩ６に含まれるバナジウムはＶ４ +として３６％及びＶ５ +として６４％の割合で存在した。従って多金属酸化物ＶＭＩ６はＭｏ9.6Ｖ2.4Ｏ34.37の化学量論を有した。
【０１０２】
所属のＣｕ−Ｋα粉末Ｘ線回折スペクトルの視覚的現象パターンはＭＩ１のパターンに相当し（図１４参照）、ＭＩ１と共通の原子の空間配置を示す。ＭＩ１と同様に実施した評価により、重要な２θ範囲で以下の回折線を生じた。
【０１０３】
【表１８】
【表１９】
ＭＩ７：Ｍｏ9.6Ｖ2.4Ｏ34.13
ＭＩ６のために製造した、噴霧乾燥した粉末１００ｇを、等温加熱した石英球容量１ｌを有する水平の回転炉中で、回転速度１２rpmで、以下の条件下で焼成した。第１段階で、装入した粉末を５０分以内で２５℃から２７５℃に加熱し、第１段階に直接続く第２段階で、装入した粉末を２５分以内で連続的に２７５℃から３００℃に加熱し、直接続く第３段階で、装入した粉末を３００℃でなお４時間保持した。引き続き回転炉の外部加熱を中断し、回転球に空気を吹き付けることにより冷却した。その際装入した粉末を３時間以内で室温（２５℃）に冷却した。（冷却段階を含めた）全焼成時間の間、石英球に５０Ｎｌ／ｈの空気流を貫流した。
【０１０６】
生じた粉末状の多金属酸化物ＭＩ７は黒い色及び比表面積５.７ｍ2／ｇ（ＤＩＮ６６１３１）を有した。多金属酸化物ＭＩ６に含まれるバナジウムはＶ4+として５６％及びＶ5+として４４％の割合で存在した。従って多金属酸化物ＭＩ７はＭｏ9.6Ｖ2.4Ｏ34.13の化学量論を有した。
【０１０７】
所属のＣｕ−Ｋα粉末Ｘ線回折スペクトルの視覚的現象パターンはＭＩ１のパターンに相当し（図１５参照）、従ってＭＩ１と共通の原子の空間配置を示す。ＭＩ１と同様に実施した評価は、重要な２θ範囲で以下の回折線を生じた。
【０１０８】
【表２０】
ＭＩ８：Ｍｏ9.0Ｖ3.0Ｏ33.72
８０℃で、第１の容器中でシュウ酸二水和物３０６.８６ｇ（理想組成；Ｈ2Ｃ2Ｏ4・２Ｈ2Ｏ、Ｈ2Ｃ2Ｏ4含量：７１.４重量％）を水４ｌに溶かした。引き続き透明な水溶液中で８０℃に維持してポリバナジン酸アンモニウム１１５.４８ｇ（Ｖ2Ｏ5含量：８８.２重量％、理想組成：（ＮＨ4）2Ｖ6Ｏ16）を撹拌して溶かし、その際濃い青色の水溶液が生じた（溶液Ａ）。その際、反応バッチの泡立ちを回避するために、ポリバナジン酸アンモニウムを１５分以内で少量ずつ添加した。第２の容器中でヘプタモリブデン酸アンモニウム水和物５９４.８２ｇ（ＭｏＯ3含量：８１.３重量％、理想組成：（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ）を８０℃の温水４ｌに撹拌して溶かした（溶液Ｂ）。引き続き８０℃で溶液Ｂを１５分以内で連続的に溶液Ａに撹拌して入れた。その際生じた濃い青色の水溶液を８０℃でなお１５時間後撹拌し、引き続き噴霧乾燥した（入口温度：３１０℃、出口温度：１１０℃）。
【０１１０】
噴霧乾燥した粉末１００ｇを、等温加熱した石英球容量１ｌを有する水平の回転炉中で、回転速度１２rpmで、ＭＩ７に記載されたと同様に空気流中で焼成した。
【０１１１】
生じた粉末状の多金属酸化物ＭＩ８は黒い色及び比表面積５.３ｍ2／ｇ（ＤＩＮ６６１３１）を有した。多金属酸化物ＭＩ８に含まれるバナジウムはＶ4+として５２％及びＶ5+として４８％の割合で存在した。それとともに多金属酸化物ＭＩ８はＭｏ9.0Ｖ3.0Ｏ33.72の化学量論を有した。所属のＣｕ−Ｋα粉末Ｘ線回折スペクトルの視覚的現象パターンはＭＩ１のパターンに相当し（図１６参照）、従ってＭＩ１と共通の原子の空間配置を示す。ＭＩ１と同様に実施した評価は、重要な２θ範囲で以下の回折線を生じた。
【０１１２】
【表２１】
【表２２】
ＭＩ９：Ｍｏ9.0Ｖ3.0Ｏ34.04
ＭＩ８のために製造した、噴霧乾燥した粉末１００ｇを、等温加熱した石英球容量１ｌを有する水平の回転炉中で、回転速度１２rpmで,ＭＩ６に記載されたと同様に空気流中で焼成した。生じた多金属酸化物ＭＩ９は黒い色及び比表面積５.７ｍ2／ｇ（ＤＩＮ６６１３１）を有した。
【０１１５】
多金属酸化物ＭＩ９に含まれるバナジウムはＶ4+として３１％及びＶ5+として６９％の割合で存在した。従って多金属酸化物ＭＩ９はＭｏ9.0Ｖ3.0Ｏ34.04の化学量論を有した。所属のＣｕ−Ｋα粉末Ｘ線回折スペクトルの視覚的現象パターンはＭＩ１のパターンに相当し（図１７参照）、ＭＩ１と共通の原子の空間配置を示す。ＭＩ１と同様に実施した評価は、重要な２θ範囲で以下の回折線を生じた。
【０１１６】
【表２３】
ＶＭＩ２：Ｍｏ9.0Ｖ3.0Ｏ32.90
ＭＩ８で製造した噴霧乾燥した粉末１００ｇを、等温加熱した石英球容量１ｌを有する水平の回転炉中で、回転速度１２ｒｐｍで、ＭＩ１に記載されたと同様に焼成した。
【０１１８】
生じた多金属酸化物ＶＭＩ２は黒い色及び比表面積６.８ｍ2／ｇ（ＤＩＮ６６１３１）を有した。多金属酸化物ＶＭＩ２に含まれるバナジウムはＶ4+として９３％及びＶ3+として７％の割合で存在した。所属のＣｕ−Ｋα粉末Ｘ線回折スペクトルの視覚的現象パターンは明らかに多金属酸化物ＭＩ１のパターンと異なり（図１８参照）、２θ範囲５゜〜５０゜で以下の強い回折線を生じた。
【０１１９】
【表２４】
２）多金属酸化物ＩＩの製造
ＭＩＩ１：ドイツ特許第４４４０８９１号明細書のＭ５の出発物質１（Ｃｕ12Ｍｏ12Ｏ48）を後処理した。
【０１２１】
水５００ｍｌ中に、酸化銅（ＩＩ）５５.３ｇ（ＣｕＯ、Ｍｅｒｃｋ,Ｄａｒｍｓｔａｄｔ、純粋、最低９６％、粉末状）及び酸化モリブデン（ＶＩ）１００ｇ（ＭｏＯ3、Ｍｅｒｃｋ、Ｄａｒｍｓｔａｄｔ、分析程度、最低９９.５％、粉末状）を分散して入れた。全量の水性分散液をオートクレーブ（材料、Ｈａｓｔｅｌｌｏｙ Ｃ４、内部容量：２.５ｌ）中で撹拌して（１０００ｒｐｍ）３５０℃に加熱し、この温度及び所属する過圧で撹拌して２４時間保持した。引き続きオートクレーブを室温に冷却し、これに含まれる水性分散液を取り出し、分散した固形物を濾過し、引き続き乾燥棚中で８０℃で乾燥した。生じた乾燥粉末は走査式電子顕微鏡分析により数平均粒子直径約８μｍを有する結晶粒子を有した。結晶粒子の化学分析によりＣｕ／Ｍｏ比約１が得られた。
【０１２２】
Ｃｕ−Ｋα放射線（Siemens-Diffraktometer D-5000,40kV,30mA、自動分散、散乱及び計数管コリメータ及びペルチエ検出器を有する）を使用して、結晶粉末ＣｕＭｏＯｙは以下のＸ線回折パターンを示し、使用されるＸ線の波長に依存しない格子面間隔ｄ［Å］及び関連する、最も強い強度（幅）の回折線に対する種々の回折線の相対強度（％）の形で示される。
【０１２３】
【表２５】
【表２６】
【表２７】
格子面間隔ｄの表示の誤差は±０.２０Åである（低い強度の線にはおそらくわずかな不純物に起因する線が含まれる）、このＸ線回折パターンは、Russian Journal of Inorganic Chemistry 36 (7),1991,927頁表１に記載のＣｕＭｏＯ4−ＩＩＩに関するパターンに相当する。
【０１２７】
ＭＩＩ２：ドイツ特許第１９５２８６４６号明細書のＭ３の出発物質１（Ｃｕ12Ｍｏ6Ｗ6Ｏ42 〜 48）を後処理した。
【０１２８】
ヘプタモリブデン酸アンモニウム水和物２２３.０５ｇ（ＭｏＯ3含量：８１.３％、理想組成：（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ）及びパラタングステン酸アンモニウム水和物３２７.５２ｇ（ＷＯ3含量：８９.２重量％、理想組成：（ＮＨ4）10Ｗ12Ｏ41・７Ｈ2Ｏ）を９０℃で水５ｌに撹拌して溶かした（溶液Ａ）。酢酸銅水和物４９２.６４ｇ（Ｃｕ含量：３２.５重量％、理想組成：Ｃｕ（ＣＨ3ＣＯＯ）2・Ｈ2Ｏ）に水３ｌ及び２５重量％アンモニア水溶液１９７.８８ｇを加え、２５℃で１５分撹拌し、その際薄い青色の懸濁液が得られた（懸濁液Ｂ）。引き続き懸濁液Ｂを９０℃を有する溶液Ａに撹拌して入れ、その際生じた懸濁液を８０℃で更に３時間撹拌した。生じた懸濁液の水性懸濁媒体（懸濁液Ｃ）は２５℃に冷却後、ｐＨ値５.３（ガラス電極）を有した。懸濁液Ｃは入口温度３１０℃及び出口温度１１０℃で噴霧乾燥した。
【０１２９】
その際得られた緑色の粉末を空気中で焼成し、その際第１段階で２４時間以内で連続的に２５℃から３００℃に加熱し、これに続く第２段階で３時間以内で連続的に３００℃から７８０℃に加熱し、第３段階でなお１時間７８０℃に温度を維持した。使用可能な容量１ｌを有する回転炉中で焼成を実施し、その際出発噴霧粉末それぞれ６０ｇを使用し、空気流５０Ｎｌ／ｈを使用した。
【０１３０】
生じた粉末は褐色及びＤＩＮ６６１３１による比表面積０.３ｍ2／ｇ及びＣｕ12Ｍｏ6Ｗ6Ｏ42 〜 48の組成を有した。走査式電子顕微鏡分析により粉末は数平均粒子直径約８μｍを有する結晶粒子を有した。Ｃｕ−Ｋα放射線（Siemens-Diffraktometer D-5000,40kV,30mA、自動分散、散乱及び計数管コリメータ及びペルチエ検出器を有する）を使用して結晶粉末は粉末Ｘ線グラフを示し、これは鉄マンガン重石指紋とＨＴ−銅モリブデン酸指紋との重なりを示し、すなわち二相構造を有していた。線の強度により２つの構造タイプは約６０（鉄マンガン重石構造）：４０（ＨＴ−銅モリブデン酸タイプ）の頻度比で存在した。
【０１３１】
ＨＴ−銅モリブデン酸構造タイプは、 以下のＸ線回折グラフにより、Ｃｕ−Ｋα放射線（Siemens-Diffraktometer D-5000,48kV,30mA、自動分散、散乱及び計数管コリメータ及びペルチエ検出器を有する）を使用してＣｕＭｏ0.9Ｗ0.1Ｏ3.5 〜 4の組成の結晶粉末で表され、使用されるＸ線の波長に依存しない格子面間隔ｄ［Å］及び関連する、最も強い強度（幅）の回折線に対する（減衰強度により示される）種々の回折線の相対強度（％）の形で示される。
【０１３２】
【表２８】
【表２９】
【表３０】
格子面間隔ｄの表示の誤差は、２.９Å以上のｄ値に関しては、主に±０.３Åであり、２.９Åより小さいｄ値に関しては、±０.２Åである（低い強度の線にはおそらくわずかな不純物に起因する線が含まれる）。
【０１３６】
３）シェル型触媒Ｓ１〜Ｓ３及び比較シェル型触媒ＳＶ１〜ＳＶ３の製造
Ｓ１：１）で製造した多金属酸化物ＭＩ１（Ｍｏ8.54Ｖ2.47Ｗ0.99Ｏ33.53）を０.１〜５０μｍの範囲の粒子直径に粉砕後、その際生じた活性物質粉末を回転ドラム中で、直径４〜５ｍｍ及び４０〜２００μｍの範囲の表面粗面性Ｒｚ（ＤＩＮ４７６８、１により、Ｈｏｍｍｅｌｗｅｒｋｅ社（ドイツ）のＤＩＮ／ＩＳＯ表面積測定用Ｈｏｍｍｅｌ テスターを用いて決定した）の非孔質の、表面が粗のステアタイト球に、ステアタイト球２００ｇ当たり粉末５０ｇの量で、同時に水１８ｇを添加してドイツ特許第４４４２３４６号明細書により被覆した。引き続き１１０℃の熱い空気で乾燥した。
【０１３７】
ＳＶ１：Ｓ１と同様に実施した、ただし活性物質として、同様にＭｏ8.54Ｖ2.47Ｗ0.99Ｏ33.53の組成を有する、１）で製造した、相当する方法で粉砕した多金属酸化物ＶＭＩ１を使用した。
【０１３８】
Ｓ２：Ｓ１と同様に実施した、ただし活性物質として、１）で製造した、相当する方法で粉砕した多金属酸化物ＭＩ１（ Ｍｏ12Ｖ3.47Ｗ1.39Ｏ47.11）及び遠心分離粉砕器、Ｒｅｔｓｃｈ社（ドイツ）を使用して１〜３μｍの数平均最大粒子直径に粉砕した、２で製造した多金属酸化物粉末ＭＩＩ１（Ｃｕ12Ｍｏ12Ｏ48）からなる混合物を使用した。ＭＩＩ１をＭＩ１に、生じた混合粉末中の前記の化学量論単位のモル比が６.５（ＭＩ１）：１（ＭＩＩ１）になるような量で撹拌して入れた。強力混合機、Ｇｕｓｔａｖ Ｅｉｒｉｃｈ、Ｈａｒｄｈｅｉｍ、ドイツ（形式ＲＯ２、ＭＰＭ装置）中で混合することにより、２つの粉末の完全な混合物が得られた。容量１０ｌを有し、６４ｒｐｍで回転する槽及び槽に対して向流で９００ｒｐｍで回転するＳｔｅｒｎ羽根車を使用して、混合物６００ｇを１５分で混合した。
【０１３９】
生じた二相の活性物質は以下のものである。
【０１４０】
［Ｍｏ12Ｖ3.47Ｗ1.39Ｏ47.11］6.5［Ｃｕ12Ｍｏ12Ｏ48］≒Ｍｏ12Ｖ3Ｗ1.2Ｃｕ1.6Ｏ47.23
Ｓ３：Ｓ２と同様に実施した、ただし２）で製造した多金属酸化物ＭＩＩ１の代わりに２）で製造した多金属酸化物ＭＩＩ２を使用した。
【０１４１】
生じた活性物質は以下のものである。
【０１４２】
［Ｍｏ12Ｖ3.47Ｗ1.39Ｏ47.11］6.5［Ｃｕ12Ｍｏ6Ｗ6Ｏ42 〜 48］
ＳＶ２：Ｓ１と同様に製造した、ただし活性物質として以下のように製造した微細分散した粉末を使用した。
【０１４３】
酢酸銅（ＩＩ）一水和物１２７ｇ（Ｃｕ３２.４重量％）を水２７００ｇに溶かし、溶液Ｉを製造した。ヘプタモリブデン酸アンモニウム四水和物８６０ｇ（ＭｏＯ3８１.３重量％）、メタバナジン酸アンモニウム１４３ｇ（Ｖ2Ｏ5７７.２重量％）及びパラタングステン酸アンモニウム七水和物１２６ｇ（ＷＯ3８９.３重量％）を９５℃で順次水５５００ｇに溶かし、溶液ＩＩを製造した。引き続き溶液Ｉを直ちに溶液ＩＩに撹拌して入れ、８０℃に加熱した水性混合物を出口温度１１０℃で噴霧乾燥した。
【０１４４】
噴霧粉末８００ｇを混練し、ＭＩ１を製造する噴霧粉末８００ｇと同様に焼成した。その後粉砕して、粒子直径０.１〜５０μｍを生じ、Ｓ１と同様のシェル型触媒が形成された。
【０１４５】
活性物質の化学量論：Ｍｏ12Ｖ3Ｗ1.2Ｃｕ1.6Ｏｘ *
図１９は、２θ＝５゜〜５０゜の範囲でＡ1〜Ａ10と異なるＸ線回折線を有することにより、多金属酸化物ＭＩ１のＣｕ−Ｋα粉末のＸ線回折スペクトルと著しく異なるＣｕ−Ｋα粉末Ｘ線回折スペクトルを示す。
【０１４６】
ＳＶ３：ＳＶ２と同様に実施した、ただし全焼成時間中、空気３.６Ｎｌ／ｈのみが焼成炉を貫流した。
【０１４７】
活性物質の化学量論：Ｍｏ12Ｖ3Ｗ1.2Ｃｕ1.6Ｏｘ **
４）. ３）で製造したシェル型触媒の、アクロレインからアクリル酸を生じるための気相酸化用触媒としての使用
触媒を管型反応器（Ｖ２Ａステンレス鋼、内径２５ｍｍ、触媒床２０００ｇ、塩浴を用いて加熱した）に導入し、
アクロレイン５容量％、
酸素７容量％、
蒸気１０容量％及び
窒素７８容量％
からなる気体の混合物を、反応温度２５０〜２７０℃で、残留時間２.０秒を使用して供給した。すべての場合に、成形を終了後、１回の通過により均一のアクロレイン転化率９９％を生じるように塩浴温度を調整した。反応器に生じる生成物ガス混合物をガスクロマトグラフィーにより分析した。種々の触媒を使用してアクリル酸形成の選択率の結果を以下の表に示した。
【０１４８】
【表３１】
転化率、選択率及び残留時間を以下に示す。
【０１５０】
アクロレインの転化率Ｃ（％）＝（転化したアクロレインのモル数／装入したアクロレインのモル数）×１００
アクリル酸形成の選択率Ｓ（％）＝（アクリル酸に転化したアクロレインのモル数／すべての転化したアクロレインのモル数）×１００
滞留時間（秒）＝（触媒を充填した反応器の空間容量（ｌ）／装入した合成ガス量（Ｎｌ／ｈ））×３６００
【図面の簡単な説明】
【図１】多金属酸化物ＭＩ１の空間配置を示すＣｕＫα粉末Ｘ線回折スペクトルの図である。
【図２】前記スペクトルの２θ範囲５〜４３゜の拡大図である。
【図３】前記スペクトルの２θ範囲４３〜６５゜の拡大図である。
【図４】多金属酸化物ＭＩ３の空間配置を示すＣｕＫα粉末Ｘ線回折スペクトルの図である。
【図５】前記スペクトルの２θ範囲５〜４３゜の拡大図である。
【図６】前記スペクトルの２θ範囲４３〜６５゜の拡大図である。
【図７】多金属酸化物ＭＩ４の空間配置を示すＣｕＫα粉末Ｘ線回折スペクトルの図である。
【図８】前記スペクトルの２θ範囲５〜４３゜の拡大図である。
【図９】前記スペクトルの２θ範囲４３〜６５゜の拡大図である。
【図１０】多金属酸化物ＭＩ５の空間配置を示すＣｕＫα粉末Ｘ線回折スペクトルの図である。
【図１１】前記スペクトルの２θ範囲５〜４３゜の拡大図である。
【図１２】前記スペクトルの２θ範囲４３〜６５゜の拡大図である。
【図１３】比較多金属酸化物ＶＭＩ１の空間配置を示すＣｕＫα粉末Ｘ線回折スペクトルの図である。
【図１４】多金属酸化物ＭＩ６の空間配置を示すＣｕＫα粉末Ｘ線回折スペクトルの図である。
【図１５】多金属酸化物ＭＩ７の空間配置を示すＣｕＫα粉末Ｘ線回折スペクトルの図である。
【図１６】多金属酸化物ＭＩ８の空間配置を示すＣｕＫα粉末Ｘ線回折スペクトルの図である。
【図１７】多金属酸化物ＭＩ９の空間配置を示すＣｕＫα粉末Ｘ線回折スペクトルの図である。
【図１８】比較多金属酸化物ＶＭＩ２の空間配置を示すＣｕＫα粉末Ｘ線回折スペクトルの図である。
【図１９】製造したシェル型触媒の空間配置を示すＣｕＫα粉末Ｘ線回折スペクトルの図である。[0001]
BACKGROUND OF THE INVENTION
The present invention is directed to general formula I:
Mo12-abcVaM1 bM2 cOx (I)
[Where:
M1= W and / or Nb,
M2= Ti, Zr, Hf, Ta, Cr, Si and / or Ge,
a = 0.1-6, preferably 0.5-4.5,
b = 0 to 6, preferably 0.1 to 6, particularly preferably 0.5 to 4,
c = 0-6, often 0.1-6 or 0.5-4,
Where a + b + c = 0.1-6, preferably 0.5-4.5, and
x = a numerical value determined by the valence and frequency of an element different from oxygen in Formula I
The multi-metal oxide has a three-dimensional atomic arrangement obtained by using Cu—Kα radiation (λ = 1.54178Å) of 5 to 50 °. In the 2θ range (expressed in units of in-plane angles), at least the following characteristic characteristic diffraction lines A1, AThree, AFive, A9And ATenHowever, at most the following diffraction line A1~ ATenX-ray powder diffraction spectrum (diffracted X-ray intensity A plotted as a function of double diffraction angle (2θ)):
[0002]
[Table 5]
It is related with the polymetal oxide characterized by producing.
[0004]
In this case, the wavelength λ and the diffraction angle θ of X-rays used for diffraction are Bragg's relational expressions:
2 sin θ = λ / d
[Where d is the lattice plane distance of a three-dimensional atomic arrangement belonging to each diffraction line].
[0005]
Furthermore, the present invention relates to a process for the production of multimetal oxide I and to the direct use of the multimetal oxide as an active material for the catalytic gas phase oxidation of organic compounds.
[0006]
The invention also relates to the use of multimetal oxide I as a starting compound for the production of multimetal oxide materials containing Mo and V, which are suitable as active materials for the catalytic gas phase oxidation of organic compounds. .
[0007]
It is known to produce a multi-metal oxide material containing Mo and V and to use the multi-metal oxide material as an active material for the catalytic gas phase oxidation of organic compounds (eg European Patent Application No. 293859). No. description).
[0008]
Initially, such multi-metal oxide materials containing Mo and V provide suitable sources (starting compounds) from each of their elemental components and are as complete as possible from the total amount of these sources, advantageously Produces a dry material composed corresponding to the required stoichiometric amount of the fine, desired multi-metal oxide material, and this dry mixture contains inert gas or oxygen for several hours at elevated temperature Produced by firing (single container method) under a gas (for example, air). In this case, what is important for the elemental source of the multi-metal oxide material is that they are already oxides or compounds that can be converted to oxides by heating in the presence of at least oxygen. (See, for example, German Offenlegungsschrift 4,335,937 and U.S. Pat. No. 4,035,262).
[0009]
Now, first, separately form a multimetal oxide containing a part of the total amount of elemental components of the desired multimetal oxide material, and then continue the desired pre-formed part of the multimetal oxide. It is also known that it is sometimes preferred to use it as a fine particle source for the production of (eg EP-A-835, DE-A-3338380, DE-A-4220659). , German Patent Application Publication No. 4307381, German Patent Application Publication No. 4405059, German Patent Application Publication No. 4405060, German Patent Application Publication No. 4405514 and German Patent Application. (See Publication No. 4440981).
[0010]
In this case, in general, a multimetal oxide material having a multiphase structure which is more advantageous for the catalytic gas phase oxidation of organic compounds than a multimetal oxide material produced by a method known per se is produced.
[0011]
[Problems to be solved by the invention]
The object of the present invention is to use as a starting compound for the production of multimetallic oxide materials containing multiphase Mo and V, which are particularly suitable as active materials for the gas phase catalytic oxidation of acrolein to acrylic acid It was possible to provide a new partial metal oxide of a multi-metal oxide material containing Mo and V.
[0012]
[Means for Solving the Problems]
Therefore, the multimetal oxide I defined at the beginning was found. Preferred multimetal oxides I are especially those having x = 15-50. X is preferably 25 to 40, particularly preferably 30 to 40. Further, among the multi-metal oxides I, it is particularly preferable that c = 0. c = 0 and M1= When W is exclusively W, ≧ 25%, or ≧ 50%, or ≧ 75%, or ≧ 95%, or ≧ 99% of vanadium is V4+Is advantageously present as
[0013]
What is typical for the novel multimetal oxide I is that the X-ray powder diffraction spectrum obtained using its Cu-Kα radiation is at least characteristic diffracted as a fingerprint characterized in the 2θ range of 5-50 °. Line A1, AThree, AFive, A9And ATen, But never diffraction line A1, A2, AThree, AFour, AFive, A6, A7, A8, A9And ATenIt does not contain more.
[0014]
It should be noted that some of the diffraction lines have a relatively large half-width FWHM [width of the diffraction line at a height half the maximum amplitude of the diffraction line, expressed as an angle in the plane (as a function of 2θ. Plotted intensity)This reflects the anomalous pattern of the near arrangement and the far arrangement in the novel multimetal oxide I (see Examples). This near and far placementofThe special form is considered, among other things, due to the special catalytic properties of the multi-metal oxide I according to the invention, according to the inventors' view.
[0015]
Based on the special half-width, the X-ray powder diffraction spectrum of the multi-metal oxide I according to the invention is a completely unresolved diffraction line Aiincluding. However, many diffraction lines AiIs present as a relative maximum in the contour of the X-ray powder diffraction spectrum of the novel multimetal oxide I in a form that is visually directly identifiable (after removal of the linear background). Diffraction line A according to the claims hereiniIt is defined as
[0016]
After removing the linear background [A (coupling line between 2θ = 5 ° and A (2θ = 65 °)], these diffraction lines A1~ ATenFurthermore, the following diffraction line A1~ ATenRelative line strength (IA rel= (I / Io) × 100%), using the amplitude measured from the baseline to the relative maximum as the intensity measure:
[0017]
[Table 6]
With respect to this line strength data, the relative line strength, unlike the position of the line, is significantly influenced in a manner well known to those skilled in the art by the individual crystal orientations that occur based on the crystal form anisotropy in the various powder preparations. It should therefore be noted that it is not very important for the identification of new multimetal oxides.
[0019]
In this connection, according to the applicant's view, another feature of the Cu-Kα X-ray powder diffraction spectrum of the multi-metal oxide I according to the invention does not contain a diffraction line which is generally FWHS <0.25 °. It should be confirmed that it appears.
[0020]
In all examples, X-ray powder diffraction spectra were recorded using a Siemens Diffraktometer D-5000 using Cu-Kα radiation (40 kV, 30 mA, λ = 1.54178Å). . The diffractometer was equipped with automatic primary and secondary collimators and a graphite secondary monochromator.
[0021]
Of course, the resolution of the X-ray powder diffraction spectrum of polymetal oxide I, and thus the selective characterization, can be achieved by removing the linear background and then calculating the experimental diffraction spectrum (with its mathematical function) under the boundary condition of the minimum mean square deviation. Line A which describes the envelope) and decomposes it separately1 *~ ATen*This can be done by developing the superposition. Each of the resolved line maxima defines their line position.
[0022]
The mathematical decomposition of the X-ray powder diffraction spectrum already described was carried out using the 1994 version of the software-package DIFFRAC-AT V 3.2 / PROFILE procured from Siemens, in which case the decomposition and fitting was Pearson VII. This was done based on the Pearson-VII-form function.
[0023]
Diffraction line A in Cu-Kα powder X-ray powder diffraction spectrum of multimetal oxide I according to the present invention2, AFourAnd A6~ A8The existence of these envelopes based solely on visual observation is partially linked to some degree of uncertainty and, in some cases, controversial (see the examples), as described above. The mathematical decomposition obtained is generally without question the diffraction line A2 *, AFour*, A6 *And A7 *(See Example), whereas diffraction line A8 *Is unnecessary. Thus, both characterization methods (information) together require the definitions set forth in the subject claims of the present invention. In contrast, exclusively by mathematical decomposition, the Cu-Kα powder X-ray powder diffraction spectrum of the multi-metal oxide I according to the present invention can generally be characterized as follows:
[0024]
[Table 7]
In this case IF rel[%] Is diffraction line A1 *~ ATen*Is the percentage of the intensity of the diffraction line relative to the maximum intensity of, where the area under the diffraction line is used as an intensity measure.
[0026]
The multimetal oxide I according to the invention simply produces from the appropriate source of its elemental components a dry mixture of the finest possible, preferably fine particles, corresponding to the desired stoichiometric amount, the mixture Can be obtained by firing at a temperature in the range of 300 to 500 ° C. The key to obtaining the multimetal oxide I according to the invention is then the redox properties of the firing atmosphere which must not be too high oxidizing or too high reducing.
[0027]
It is not possible to provide general reasonable quantitative data on the required redox properties of the firing atmosphere. On one side, the required redox properties vary with the stoichiometric amount selected, and on the other side the opposite ion (eg NH) of the selected source of the elemental component.Four +) Is also involved in the redox properties of the firing atmosphere when it decomposes during firing. However, through pre-experiment for investigation, those skilled in the art can confirm the required redox characteristics of the firing atmosphere.
[0028]
In this case, in order to control the redox characteristics of the firing atmosphere, those skilled in the art have used, for example, N2And / or a noble gas, for example ammonia, hydrogen, low molecular aldehydes and / or hydrocarbons as reducing gas and oxygen (usually in the form of air) as oxidizing gas.
[0029]
What is important for the elemental source is simply that they are already oxides or compounds that can be converted to oxides by heating, at least in the presence of oxygen. Therefore, in addition to oxides, halides, nitrates, formates, citrates, oxalates, acetates, carbonates or hydroxides are particularly suitable as starting compounds. Suitable starting compounds of Mo, V, W and Nb are also their oxo compounds (molybdates, vanadates, tungstates and niobates), which are reducing NHs when heated.ThreeLiberates NHFour +In general as an opposite ion. Of course, acids derived from these oxo compounds are also possible starting compounds. More often, compounds such as ammonium acetate and ammonium nitrate are also added that act as pore formers during firing and also affect the redox properties of the firing atmosphere.
[0030]
Complete mixing of the starting compounds within the scope of the invention can be carried out dry or wet. When dry, the starting compound is preferably used as a fine powder and calcined after mixing and optionally compression. However, it is advantageous to carry out thorough mixing in a wet manner. In this case, it is usually advantageous to mix the starting compounds with one another in the form of an aqueous solution and / or suspension. Subsequently, the aqueous material is dried and fired after drying. Advantageously, the drying process is carried out immediately after production of the aqueous mixture and by spray drying (inlet temperature is generally between 250 and 350 ° C.R,OrThe outlet temperature is generally 100-150 ° C).
[0031]
Interestingly, the new multimetal oxides I are already gas phase catalytic oxidation of organic compounds, such as alkanes, alkanols, alkenes, alkanals, alkenals and alkenols having 3 to 6 carbon atoms (eg propylene, methacrolein, gas phase catalytic oxidation (ammoxidation) of t-butanol, methyl ester of t-butanol, iso-butane, iso-butene or iso-butyraldehyde) to olefinically unsaturated aldehydes and / or carboxylic acids and the corresponding nitriles Particularly suitable as active material for catalysts for propene to acrylonitrile and to iso-butene or t-butanol to methacrylonitrile. Examples include the production of acrolein, methacrolein and methacrylic acid. Furthermore, it is also suitable as a catalytically active material for oxidative dehydrogenation of olefinic compounds.
[0032]
In this case, the multimetal oxide I is undoubtedly suitable as an active material of the catalyst for the gas phase catalytic oxidation of acrolein to acrylic acid, and its high activity is particularly remarkable for this reaction.
[0033]
When the multi-metal oxide material according to the present invention is used as the active material of a catalyst for the gas phase catalytic oxidation of organic compounds, especially the gas phase catalytic oxidation of acrolein to acrylic acid, it can be molded into the desired catalyst form. It is preferably carried out by applying to a preformed inert catalyst support. In this case, the application can take place before or after the final calcination. In this case, customary carrier materials such as porous or non-porous aluminum oxide, silicon dioxide, thorium dioxide, zirconium dioxide, silicon carbide or silicates such as magnesium silicate or aluminum silicate can be used. The support may be regularly or irregularly shaped, with preference given to regularly shaped supports, spheres or hollow cylinders with a clearly formed surface roughness. Of these, spheres are also particularly advantageous. Particular preference is given to using a substantially non-porous, surface-rough spherical support made of steatite having a diameter of 1 to 6 mm, preferably 4 to 5 mm. The layer thickness of the active material should preferably be chosen to be in the range of 50 to 500 μm, advantageously in the range of 150 to 250 μm. More specifically, in the production of such a coated catalyst, the powder material to be applied for coating the support is generally wetted and dried again after application, for example with hot air.
[0034]
In order to produce a coated catalyst, the coating of the support is generally carried out in a suitable rotatable container, for example a container as known from DE-A 29 09 671 or EP-A 29 3859. carry out. In general, important materials are fired before carrier coating. Furthermore, the catalytically active material is ground to a particle size in the range of more than 0 and not more than 300 μm, preferably 0.1 to 200 μm, particularly preferably 0.5 to 50 μm, before carrying out the coating. Preferably, the coating step and the firing step are based on European Patent Application No. 293859, and the resulting multimetal oxide I layer has a specific surface area of 0.50 to 150 m.2/ G, specific pore volume 0.10-0.90 cmThree/ G, and a pore diameter distribution such that at least 10% of the pore volume each is distributed in the diameter range 0.1- <1 μm, 1.0- <10 μm and 10-100 μm. It is also possible to adjust to the pore diameter distribution mentioned as advantageous in EP-A-2 93859.
[0035]
Of course, the multimetal oxide I according to the invention can also be used as a catalyst without support. In this case, a completely dry mixture consisting of the starting compound of the multimetal oxide I is advantageously compressed directly into the desired catalyst form (eg pelleting or extrusion). In this case, customary auxiliaries, for example graphite or stearic acid, may be used as lubricants and / or molding auxiliaries and from glass, asbestos, silicon carbide or potassium titanate.RuReinforcing agents such as microfibers can be added. Baking following the compression. In this case as well, it can generally be fired before molding.
[0036]
An advantageous support-free catalyst form is a hollow cylinder having an outer diameter and length of 2 to 10 mm and a wall thickness of 1 to 3 mm.
[0037]
In general, acrolein produced by catalytic gas phase oxidation of propene is used for catalytic gas phase oxidation of acrolein to acrylic acid using the novel multimetal oxide I as the catalytically active material. In general, a reaction gas containing acrolein obtained from this propene oxidation and not subjected to intermediate purification is used. Usually, the gas phase catalytic oxidation of acrolein is carried out as a heterogeneous solid bed oxidation in a tube bundle reactor. As oxidant, oxygen is used in a manner known per se, preferably diluted with an inert gas (for example in the form of air). Suitable diluents are for example N2, CO2Hydrocarbons such as methane, ethane, propane, butane and / or pentane, recycled reaction gases and / or steam. In general, during acrolein oxidation, the volume ratio of acrolein: oxygen: water vapor: inert gas is 1: (1-3) :( 0-20) :( 3-30), preferably 1: (1-3 ): (0.5 to 10): Adjust to (7 to 18). The reaction pressure is generally from 1 to 3 bar and the total space velocity is preferably from 1000 to 3500 Nl / l / h. Typical multitubular fixed bed reactors are described, for example, in the publications DE-A 2830765, DE-A 22015528 or U.S. Pat. No. 3,147,084. Has been. The reaction temperature is usually chosen such that the acrolein conversion is 90% or more, preferably 98% or more in a single pass. Usually, this requires a reaction temperature of 230-330 ° C.
[0038]
It should be noted that the multimetal oxide I according to the invention has not only high activity but also a surprisingly short forming time in the catalytic gas phase oxidation of acrolein to acrylic acid, ie the multimetal oxide according to the invention. When the tube bundle reactor loaded with I is operated for the oxidation formation of acrylic acid using a gas stream containing acrolein under the specified conditions, the selectivity of acrylic acid formation is already within its short operating time. Reach value. With respect to this plateau value, the production of the multi-metal oxide material according to the invention is highly reproducible.
[0039]
However, while maintaining the above advantages, the multimetal oxide I is not fully capable of being a catalytically active material for the catalytic gas phase oxidation of organic compounds, particularly acrolein to acrylic acid, for the first time in the following cases: Demonstrated. That is, the capability is that the multimetal oxide I is represented by the general formula
MThree 12CudHeOy (II)
[Where:
MThree= Mo, W, V, Nb and / or Ta,
d = 4-30, preferably 6-24, particularly preferably 9-17,
e = 0 to 20, preferably 0 to 10 and
y = a numerical value determined by the valence and frequency of an element different from oxygen in Formula II
Is diluted with a fine multi-metal oxide of formula III,
[A]p[B]q (III)
[Where:
[0040]
[Equation 3]
B = MThree 12CudHeOy (Promoter phase),
p, q = 0, a ratio p / q of 160: 1 to 1: 1, preferably 20: 1 to 1: 1, particularly preferably 15: 1 to 4: 1. Have
Ingredient [A]pA chemical composition that extends three-dimensionally and is bounded by a different chemical composition from its local surroundings:
A Mo12-abcVaM1 bM2 cOx
In the form of region A and
Ingredient [B]qA chemical composition that extends three-dimensionally and is bounded by a different chemical composition from its local surroundings:
B MThree 12CudHeOy
In this case, at least two-phase multi-metal oxide material is distributed in such a manner that the regions A and B are distributed in a mixture of the particulate A and the particulate B relative to each other. Achieved in manufacturing.
[0042]
In order to produce such a multi-metal oxide material III, it is particularly simple that the multi-metal oxides I and II are produced separately separately and then at least one fine, separately pre-manufactured multi-metal. A complete dry mixture of oxide I and at least one fine, separately pre-manufactured multimetal oxide II is produced in the desired mixing ratio (in this case, complete mixing can be carried out wet or dry; wet , Generally if carried out in aqueous form, followed by drying; the mixing can be carried out in a kneader or mixer), and then from the completely dry mixture by molding in the same way as described only for the multimetal oxide I Suitable catalysts can be prepared for the catalytic gas phase oxidation of organic compounds, in particular the catalytic gas phase oxidation of acrolein to acrylic acid. Of course, however, both the multimetal oxide I and the multimetal oxide III can be used as catalysts in the form of powders. Likewise, of course, the multimetal oxide material III can be used for all the catalytic gas phase oxidations described as also applying the multimetal oxide I. When a catalyst based on the multimetal oxide material III as active material is used for the catalytic gas phase oxidation of acrolein to acrylic acid, the oxidation is generally the corresponding single use of the multimetal oxide I catalyst. Perform under the same operating conditions as described for.
[0043]
The multimetal oxide II can be produced as follows by a simple method well known to those skilled in the art. A dry mixture as complete as possible, preferably as fine as possible, is produced from a suitable source of the elemental constituents of the multimetal oxide II, and the mixture is 200-1000 ° C., often 250-600 ° C., most often 300-500 ° C. Firing at a temperature of In this case, calcination is carried out, for example, as described in German Patent Application No. 4335973.2), Mixtures of inert gas and oxygen (eg air), reducing gases such as hydrocarbons (eg methane), aldehydes (eg acrolein) or ammonia, and also O2And a reducing gas (for example, all those mentioned above). It should be noted that in this case as well, the firing atmosphere may contain water vapor. When performing calcination under reducing conditions, care should be taken not to reduce the metal component to the element. In general, the higher the firing temperature, the shorter the firing time.
[0044]
With respect to the source of the multimetal oxide II, substantially the same applies as for the source of the elemental component of the multimetal oxide I. What is also important here is that the source is already an oxide or a compound that can be converted to an oxide by heating in the presence of at least oxygen. In a preferred process variant for the production of multimetal oxides II, the complete mixture of starting compounds used is carried out in an autoclave in the presence of water vapor with an overpressure at a temperature higher than 100 and below 600 ° C.
[0045]
Based on the firing conditions selected each time, the resulting multimetal oxide II has various three-dimensional atomic arrangements. In particular, for the purposes of the present invention, all the polymetallic oxides II described as possible basic phases or promoter phases in German Offenlegungsschrift 4405514 and German Offenlegungsschrift 19528646. Is applicable. That is, the preferred multimetal oxide II has, in particular, at least one structural type (X-ray diffraction pattern) of copper molybdate listed in the following table (indicated in parentheses is the associated X-ray). Represents a source for diffractive fingerprints):
[0046]
[Table 8]
The recommended multimetal oxide II for preparing a multimetal oxide material III particularly suitable for the catalytic gas phase oxidation of acrolein to acrylic acid is the general formula IV:
CuMoAWBVCNbDTaEOY・ (H2O)F (IV)
[Where:
1 / (A + B + C + D + E) = 0.7 to 1.3
F = 0 to 1,
B + C + D + E = 0 to 1 and
Y = a numerical value determined by the valence and frequency of an element different from oxygen in formula IV
And its three-dimensional atomic arrangement is defined in Russian Jounal of Chmistry 36 (7) (1991), 921, Table 1 and German Patent Application Publication No. 4405514 and German Patent Examples thereof are those described in WO 4444091 as Wolframit.
[0048]
Of the multimetal oxides IV, the stoichiometric formula V:
CuMoAWBVCOY (V)
[Where:
1 / (A + B + C) = 0.7 to 1.3,
A, B, C = all greater than 0, provided that B + C ≦ 1,
Y = Numerical value determined by the valence and frequency of an element different from oxygen in Formula V
And the stoichiometric formula VI:
CuMoAWBOY (VI)
[Where:
1 / (A + B) = 0.7-1.3,
A / B, C = 0.01 to 10, preferably 0.01 to 1 and
Y = a numerical value determined by the valence and frequency of an element different from oxygen in Formula VI
What should be noted is. The production methods for multimetal oxides IV, V and VI are shown in German Offenlegungsschrift 4405514 and German Offenlegungsschrift 4440891.
[0049]
Further particularly preferred multimetal oxides II are those of the general formula VII:
CuMoA ′WB ′VC ′NbD ′TaE ′OY ′ (VII)
[Where:
1 / (A ′ + B ′ + C ′ + D ′ + E ′) = 0.7 to 1.3, preferably 0.85 to 1.15, particularly preferably 0.95 to 1.05, very particularly preferably Is 1,
(B ′ + C ′ + D ′ + E ′) / A ′ = 0.01 to 10, preferably 0.05 to 3, particularly preferably 0.075 to 1.5 and
Y ′ = a value determined by the valence and frequency of an element different from oxygen in formula VII
And the structural type is that of the HT-Cu molybdate type described in German Offenlegungsschrift DE 19528646.
[0050]
In this case, among the multi-metal oxides VII, C ′ + D ′ + E ′ = 0 is also advantageous. Particularly recommended VII as multimetal oxide II is the composition:
Mo10.8W1.2Cu12O42-48
It is what has.
[0051]
Furthermore, possible multimetal oxides II include mixtures of multimetal oxides IV and VII as disclosed in German Offenlegungsschrift DE 19528646. This is especially true for those containing multimetallic oxides IV and VII in intergrowth form.
[0052]
Of course, the mixture prepared from the separately prepared fine multimetal oxides I and II is first compressed, then ground to produce a multimetal oxide III catalyst before its use, and then the desired catalyst for the first time. It can also be processed into a shape. In this case, for the maximum particle diameter, as in the case of the separately prepared multimetal oxides I and II, more than 0 and not more than 300 μm, particularly preferably 0.5 to 50 μm, quite particularly A diameter range of 1 to 30 μm is preferably recommended.
[0053]
A particular advantage of the multiphase multimetal oxide material III catalyst according to the invention is that the calcination conditions necessary for obtaining the various phases are generally different from one another. Due to the separate pre-manufacturing principle, the respective firing conditions can be optimally adapted to the desired phase.
[0054]
Multi-metal oxides I are quite common beyond the above-mentioned applications, for example German Offenlegungsschrift 4,335,973, U.S. Pat. No. 4,035,262, German Offenlegungsschrift 4,405,058. Description, German Patent Application Publication No. 4405059, German Patent Application Publication No. 4405060, German Patent Application Publication No. 4405514, German Patent Application Publication No. 4440891 and German Patent It is suitable for improving the performance of the catalytically active multi-metal oxide material described in JP-A-19528646.
[0055]
For this purpose, simply the active material described in the above publication is mixed in fine form with the fine multimetal oxide I and similar to the complete starting mixture for producing the multimetal oxide material III catalyst. To form.
[0056]
In particular, the multimetal oxides I are described in German Patent Application Publication No. 4405558, German Patent Application Publication No. 4405059, German Patent Application Publication No. 4405060, German Patent Application Publication No. 4405514. And the co-phase component of the multiphase multimetal oxide material catalyst disclosed in German Patent Application No. 4440891. Furthermore, the multimetal oxide I is suitable as a component of the active phase of the multiphase multimetal oxide material catalyst described in German Offenlegungsschrift 19528646. In all of these cases, a multi-phase multi-metal oxide material catalyst containing a fine (more than 0 and not more than 300 μm) homogeneously distributed multi-metal oxide I phase is produced. These are particularly suitable as catalysts for the catalytic gas phase oxidation of organic compounds described in the respective references cited above.
[0057]
Finally, it should be noted that pure multimetal oxides I can be produced for the first time by the present invention.
[0058]
【Example】
1) Production and identification of multimetal oxides MI1-MI9 and comparative multimetal oxides VMI1 and VMI2 according to the invention
General explanation
The multimetallic oxide I according to the invention described below always contains the elemental components Mo and W in the
[0059]
Each 0.15 g of the oxide sample material is heated to 5 ml of concentrated phosphoric acid (density ρ = 1.70 g / cm at 20 ° C.Three) And 10 ml of aqueous sulfuric acid (argon atmosphere). The sulfuric acid aqueous solution used was the same amount of water and concentrated sulfuric acid (ρ20= 1.52 g / cmThree(Capacity indication relates to 20 ° C.). The solvent was selected so that the possible oxidation state of V did not fluctuate and this was tested according to the corresponding V standard.
[0060]
V5+To analyze the content, a freshly prepared and the resulting solution was added to 0.1 molar aqueous ammonium iron sulfate standard solution ((NHFour)2Fe (SOFour)2). V3+And V4+A new solution prepared by an appropriate method was newly prepared, and 0.02 molar potassium permanganate standard aqueous solution (KMnOFour) And two potential jumps occurred (V3+→ V4+And V4+→ V5+). V measured as above3+Content, V4+Content and V5+The total content must correspond to the total V content of the sample. This could also be measured by volumetric analysis using the final point display of potentiometric titration.
[0061]
For this purpose, 0.15 g of the oxide sample material is heated under heating with 10 ml of the semi-concentrated aqueous sulfuric acid solution and 10 ml of concentrated nitric acid (ρ20= 1.52 g / cmThree) Was dissolved in an argon atmosphere. Subsequently, the resulting solution was heated to evaporate part of the nitric acid and the sulfuric acid used and concentrated it to a residual volume of about 3 ml, at which time all V components were transferred to the
[0062]
The aqueous solution thus obtained was titrated with a newly prepared 0.02 molar potassium permanganate standard aqueous solution, and two potential jumps occurred. The first potential jump is the excess Fe used.2+And the second potential jump is V4+To V5+Amount of KMnO required to oxidize toFourWhich corresponds to the total V content of the sample.
[0063]
MI1: Mo8.54V2.47W0.95O33.53
Heptamolybdate hydrate 33.746 kg (MoOThreeContent: 81.8% by weight, ideal composition: (NHFour)6Mo7Otwenty four・ 4H2O), ammonium metavanadate 6.576 kg (V2OFiveContent: 76.5% by weight, ideal composition: NHFourVOThree), Ammonium paratungstate hydrate 5.764 kg (WOThreeContent: 89.0% by weight, ideal composition: (NHFour)TenW12O41・ 7H2O) and 7.033 kg of ammonium acetate (CHThreeCOONHFourContent: 97.0% by weight, ideal composition: CHThreeCOONHFour) Was dissolved in 250 l of water sequentially in the above order at a temperature of 90 ° C. The resulting yellow to orange solution was cooled to 80 ° C. and spray dried at an inlet temperature of 300 ° C. and an outlet temperature of 110 ° C.
[0064]
800 g of the resulting spray powder was kneaded for 1 hour with the addition of 250 g of water in a kneader having an effective volume of 2.5 l (form: LUK 2.5, Werner und Pfleiderer, 7000 Stuttgart, Germany). At that time, 180 g of 250 g of water was added to the kneaded material within the first 10 minutes and 70 g was added to the kneaded material within the remaining 50 minutes. The resulting wet mass kneaded product was dried for 15 hours at a temperature of 110 ° C. and then compressed with a sieve having a mesh width of 5 mm.
[0065]
Subsequently, 100 g of the granule produced at that time was fired at a rotational speed of 12 rpm in a horizontal rotary furnace having a volume of 1 liter of quartz sphere heated isothermally. At that time, firing conditions were formed as follows.
[0066]
1st stage: The charged granule is continuously heated from 25 ° C. to 275 ° C. within 50 minutes,
Second stage: The charged granules are continuously heated from 275 ° C. to 325 ° C. within 30 minutes,
Third stage: The charged granules are held at 325 ° C. for 4 hours.
4th stage: The charged granules are continuously heated from 325 ° C. to 400 ° C. within 30 minutes.
5th stage: The charged granule is held at 400 ° C. for 10 minutes.
[0067]
Subsequently, the external heating of the rotary furnace was interrupted, and the furnace was cooled by blowing ambient air from the outside. The granule charged at that time was cooled to 25 ° C. within 5 hours.
[0068]
During each firing step, a gas mixture having the following composition was allowed to flow through the internal space of the rotary furnace in parallel with the rotation axis (standard temperature and pressure condition (N) = 1 atm, 25 ° C.).
[0069]
Air 3.6 Nl / h, NHThree1.5 Nl / h and N244.9 Nl / h
(Total gas flow rate: 50 Nl / h).
[0070]
Fourth stage, fifth stage and cooling stage:
Air 3.6 Nl / h and N244.9 Nl / h
(Total gas flow rate: 48.5 Nl / h).
[0071]
The resulting powdery multimetal oxide MI1 has a black color and a specific surface area of 15.0 m.2/ G (according to DIN 66131, gas adsorption by Brunauer-Emmet-Teller (BET) (N2). Vanadium contained in the multimetal oxide MI1 is V.4+More than 99% (measured as above). Therefore, the multi-metal oxide MI1 is Mo8.54V2.47W0.99O33.53Of stoichiometry.
[0072]
The Cu-Kα powder X-ray diffraction spectrum measured by the examples and evaluated after removing the linear background had the following diffraction lines in the important 2θ range (5 ° -50 °).
[0073]
[Table 9]
[Table 10]
A Cu-Kα powder X-ray diffraction spectrum measured by an experiment reflecting the spatial arrangement of atoms of the multimetal oxide MI1 is shown in FIG. 1 (vertical axis: intensity, indicated as an absolute value, horizontal axis: 2θ range of 5 ° to 5 °). 65 °).
[0076]
Further, FIG. 1 shows a linear background (connection of A (2θ = 5 °) and A (2θ = 65 °)) and an individual diffraction curve A to be attenuated within the evaluation frame.iIndicates the position. The point of contact between the reference line and the X-ray diffraction spectrum distributes the diffraction spectrum in two natural ranges of 2θ ranges of 5 ° to 43 ° and 43 ° to 65 °.
[0077]
FIG. 2 is an enlarged view of the 2θ range 5 ° to 43 ° of the Cu-Kα powder X-ray diffraction spectrum of the multimetal oxide MI1. Furthermore, FIG. 2 shows the results of mathematical fitting and resolution performed in this range (including the background line) (PROFILE, Pearson-VII profile function, fixed background). Mathematically formed diffraction line Ai *This overlaps with the experimental outline.
[0078]
FIG. 3 shows the resolution performed in this range, including the 2θ range 43 ° -65 ° expanded in a corresponding manner and linear background lines.
[0079]
The rectangular cross section seen above the original X-ray diffraction spectrum of FIGS. 2 and 3 shows the experimental contour line of the powder X-ray diffraction spectrum and the difference line of its mathematical fit, respectively. This difference is a measure of good fit.
[0080]
MI2: Mo8.54V2.47W0.99O33.53
Granules were produced in the same manner as MI1. 400 g of granules were calcined in a calcining furnace operating on the principle of a jet reactor. The granule charged at that time was present on the wire mesh with a deposition height of 5 cm, and the gas mixture was allowed to flow through it from below. The furnace capacity was 3 l and the circulation ratio (ratio of the circulating gas mixture volumetric flow to the newly supplied gas mixture volumetric flow) was selected to be 20. The charged granules were first heated continuously from 25 ° C. to 325 ° C. within 1 hour in the furnace. Subsequently, the charged granules were held at 325 ° C. for 4 hours. At the start of firing, the gas mixture flowing through is N2120 Nl / h,
[0081]
A powdered multimetal oxide MI2 is obtained, which is represented by V5+Analysis, V4+Analysis, V3+The analysis and the X-ray diffraction spectrum of the Cu-Kα powder were the same as for the multimetal oxide MI1.
[0082]
MI3: Mo8.35V2.60W1.05O33.40
852.78 g ammonium heptamolybdate hydrate (MoOThreeContent: 81.0% by weight, ideal composition: (NHFour)6Mo7Otwenty four・ 4H2O), ammonium metavanadate 177.14 g (V2OFiveContent: 77.0% by weight, ideal composition: NHFourVOThree) And 156.29 g ammonium paratungstate hydrate (WOThreeContent: 89.0% by weight, ideal composition: (NHFour)TenW12O41・ 7H2O) was dissolved successively in 5 l of water in the above sequence at a temperature of 95 ° C. The resulting yellow to orange solution was cooled to 80 ° C. and spray dried at an inlet temperature of 300 ° C. and an outlet temperature of 110 ° C. Subsequently, 100 g of the spray-dried powder was calcined in a horizontal rotary furnace with a 1 l quartz-ball volume heated isothermally at a rotational speed of 12 rpm under the conditions defined below. In the first stage, the charged powder is continuously heated from 25 ° C. to 275 ° C. within 50 minutes, and in the second stage directly following the first stage, the charged powder is continuously heated to 275 within 30 minutes. In the third stage directly following the second stage, the charged powder is held at 325 ° C. for 4 hours, and in the fourth stage directly following the third stage, the charged powder is heated to 3.325 ° C. Heated from 325 ° C. to 400 ° C. within 5 hours. During the first three stages, quartz spheres are filled with air 9.6 Nl / h, NH33 Nl / h and N2A gas mixture consisting of 87.4 Nl / h (total gas flow rate: 100 Nl / h) was passed through. During the fourth stage, the quartz spheres are filled with air 9.6 Nl / h and N2A gas mixture consisting of 87.4 Nl (total gas flow rate: 97 Nl / h) was passed through. After completion of the fourth stage, external heating of the rotary furnace was interrupted, and cooling was performed by blowing air from the outside. In this case, the charged powder flows through the quartz sphere without change, air 9.6 Nl / h and N2It was cooled to 25 ° C. within 5 hours under a gas mixture consisting of 87.4 Nl / h.
[0083]
The resulting powdery multimetal oxide MI3 has a black color and a specific surface area of 0.5 m.2/ G (DIN 66131). Vanadium contained in the multimetal oxide MI3 is V4+More than 99%. Therefore, the multi-metal oxide MI3 is Mo8.35V2.60W1.05O33.40Of stoichiometry.
[0084]
The associated Cu-Kα powder X-ray diffraction spectra are shown in FIGS. The spatial arrangement of atoms in common with MI1 is shown. Evaluation performed in the same manner as MI1 produced the following diffraction lines in the important 2θ range.
[0085]
[Table 11]
[Table 12]
MI4: Mo8.35V2.60W1.05O33.40
A spray-dried powder was produced as in MI3. Subsequently, 60 g of the spray-dried powder were calcined in a horizontal rotary furnace with an isothermally heated quartz sphere capacity of 1 l at a rotational speed of 12 rpm and under the conditions defined below. In the first stage, the charged powder is heated from 25 ° C. to 275 ° C. within 50 minutes, and in the second stage directly following the first stage, the charged powder is continuously heated from 275 ° C. to 325 ° C. within 30 minutes. In the third stage directly following the second stage, the charged powder is held at 325 ° C. for 3 hours, and in the fourth stage directly following the third stage, the charged powder is 325 within 90 minutes. The mixture was heated from 400 ° C. to 400 ° C. and kept at 400 ° C. after 10 minutes. During the first three stages, quartz spheres are filled with air 4.8 Nl / h, NHThree1.5 Nl / h and N2A gas mixture consisting of 43.7 Nl / h (total gas flow rate: 50 Nl / h) was passed through. During the 4th and 5th stages, the quartz sphere has air 4.8 Nl / h and N2A gas mixture consisting of 43.7 (standard) l / h (total gas flow rate: 48.5 Nl / h) was passed through. After completion of the fifth stage, external heating of the rotary furnace was interrupted, and cooling was performed by blowing air from the outside. At this time, the charged powder flows through the quartz sphere without change, and the air is 4.8 Nl / h and N2It was cooled to 25 ° C. within 5 hours under a gas mixture consisting of 43.7 Nl / h.
[0088]
A powdered multimetal oxide MI4 is obtained, which is represented by V5+Analysis, V4+Analysis, V3+It was the same as the multimetal oxide MI3 in terms of analysis and in terms of Cu-Kα powder X-ray diffraction spectrum. The quantitative evaluation of the X-ray diffraction spectra (shown in FIGS. 7 to 9) carried out as described above produced the following diffraction lines in the important 2θ range.
[0089]
[Table 13]
[Table 14]
MI5: Mo8.54V2.47W0.99O33.01
800 g of spray powder formed to produce MI1 are mixed with 80 g of acetic acid (100%) and water in a kneader (type: LUK2.5, Werner und Pfleiderer, 7000 Stuttgart, Germany) with an effective volume of 2.5 l. 200 g was added and kneaded for 1 hour. At that time, 80 g of acetic acid and 80 g of water were added to the kneaded product in the first 10 minutes. The remaining 120 g of water was added to the kneaded mixture for the remaining 50 minutes. The resulting wet mass kneaded product was dried for 15 hours at a temperature of 110 ° C. and then compressed with a sieve having a mesh width of 5 mm. The granule 100 g produced at that time was subsequently fired in a horizontal rotary furnace as described in MI1.
[0092]
The resulting powdery multimetal oxide MI5 has a black color and a specific surface area of 16.0 m.2/ G (DIN 66131). Vanadium contained in the multimetal oxide MI5 is V3+As 42% and V4+As a proportion of 58%. Therefore, the multimetal oxide MI5 is different from the multimetal oxide MI1 and Mo8.54V2.47W0.99O33.01Of stoichiometry. Nevertheless, the Cu-Kα powder X-ray diffraction spectrum measured and evaluated in the same manner as for the multimetal oxide MI1 reflected the same spatial arrangement of atoms as the multimetal oxide MI1 with respect to the multimetal oxide MI5 (FIG. 10). ~ 12). The measured diffraction lines are as follows in the important 2θ range (5 ° -50 °).
[0093]
[Table 15]
[Table 16]
VMI1: Mo8.54V2.47W0.99O34.18
In order to produce MI5, 100 g of granules obtained by kneading the spray powder with water and acetic acid were calcined in a horizontal rotary furnace as described in Example MI1. However, instead of the various gas mixtures, a corresponding amount of pure air flowed through the rotary furnace.
[0096]
The resulting powdery multimetal oxide VMI1 has a black color and a specific surface area of 16.2 m.2/ G (DIN 66131). Vanadium contained in the multimetal oxide VMI1 is V4 +As 47% and V5 +As a proportion of 53%. Therefore, the multi-metal oxide VMI1 is different from the multi-metal oxides MI1 and MI5 and Mo8.54V2.47W0.99O34.18Of stoichiometry. The associated Cu-Kα powder X-ray diffraction spectrum is shown in FIG. This is clearly different from the spectrum of the multi-metal oxide MI1 and has a strong diffraction line in the 2θ range of 5 ° to 50 °, for example (with a much lower half-width):
[0097]
[Table 17]
That is, the spatial arrangement of atoms of the multimetal oxide VMI1 does not correspond to the arrangement of the multimetal oxide MI1 or MI5.
[0099]
MI6: Mo9.6V2.4O34.37
At 80 ° C., 239.74 g of oxalic acid dihydrate (ideal composition: H2C2OFour・ 2H2O, H2C2OFourContent: 71.4% by weight) was dissolved in 4 l of water. Subsequently, 90.22 g of ammonium polyvanadate (V2OFiveContent: 88.2% by weight, ideal composition: (NHFour)2V6O16) Was dissolved by stirring, whereby a deep blue aqueous solution A was formed. At that time, ammonium polyvanadate was added in small portions within 15 minutes to avoid bubbling of the reaction batch. 619.60 g ammonium heptamolybdate hydrate (MoOThreeContent: 81.3 wt%, ideal composition: (NHFour)6Mo7Otwenty four・ 4H2O) was dissolved by stirring in 4 l of warm water at 80 ° C. (solution B). Subsequently, at 80 ° C., solution B was continuously stirred into solution A within 15 minutes. The resulting dark blue aqueous solution was stirred at 80 ° C. for another 15 hours and then spray-dried (inlet temperature: 310 ° C., outlet temperature: 110 ° C.).
[0100]
100 g of the spray-dried powder was calcined in a horizontal rotary furnace having a quartz sphere capacity of 1 l heated isothermally at a rotational speed of 12 rpm under the following conditions. In the first stage, the charged powder is continuously heated from 25 ° C. to 275 ° C. within 50 minutes, and in the second stage directly following the first stage, the charged powder is continuously heated within 275 minutes within 35 minutes. C. to 325.degree. C., followed by a third step directly followed by holding at 325.degree. C. for 4 hours. Immediately thereafter, the charged powder was heated from 325 ° C. to 400 ° C. within 35 minutes in the fourth stage and held at 400 ° C. for 10 minutes in the subsequent fifth stage. Subsequently, the external heating of the rotary furnace was interrupted, and the quartz sphere was cooled by blowing air from the outside. At this time, the charged powder was cooled to room temperature (25 ° C.) within 5 hours. A 50 Nl air flow was passed through the quartz sphere during the entire firing time (including the cooling phase).
[0101]
The resulting powdery multimetal oxide MI6 has a black color and a specific surface area of 6.6 m.2/ G (DIN 66131). Vanadium contained in the multimetal oxide VMI6 is V4 +As 36% and V5 +As a proportion of 64%. Therefore, the multimetal oxide VMI6 is Mo9.6V2.4O34.37Of stoichiometry.
[0102]
The visual phenomenon pattern of the associated Cu-Kα powder X-ray diffraction spectrum corresponds to the MI1 pattern (see FIG. 14), and shows a spatial arrangement of atoms in common with MI1. Evaluation performed in the same manner as MI1 produced the following diffraction lines in the important 2θ range.
[0103]
[Table 18]
[Table 19]
MI7: Mo9.6V2.4O34.13
100 g of spray-dried powder produced for MI6 was calcined in a horizontal rotary furnace with an isothermally heated quartz sphere capacity of 1 l at a rotational speed of 12 rpm under the following conditions: In the first stage, the charged powder is heated from 25 ° C. to 275 ° C. within 50 minutes, and in the second stage directly following the first stage, the charged powder is continuously added from 275 ° C. to 300 ° C. within 25 minutes. In the third stage directly followed, the charged powder was kept at 300 ° C. for another 4 hours. Subsequently, external heating of the rotary furnace was interrupted, and cooling was performed by blowing air onto the rotating sphere. At this time, the charged powder was cooled to room temperature (25 ° C.) within 3 hours. A 50 Nl / h air stream was passed through the quartz sphere during the entire firing time (including the cooling step).
[0106]
The resulting powdery multimetal oxide MI7 has a black color and a specific surface area of 5.7 m.2/ G (DIN 66131). Vanadium contained in the multimetal oxide MI6 is V4+As 56% and V5+As a percentage of 44%. Therefore, the multimetal oxide MI7 is Mo9.6V2.4O34.13Of stoichiometry.
[0107]
The visual phenomenon pattern of the associated Cu-Kα powder X-ray diffraction spectrum corresponds to the pattern of MI1 (see FIG. 15), and thus shows a spatial arrangement of atoms in common with MI1. Evaluation performed in the same manner as MI1 produced the following diffraction lines in the important 2θ range.
[0108]
[Table 20]
MI8: Mo9.0V3.0O33.72
At 80 ° C., 306.86 g of oxalic acid dihydrate (ideal composition; H2C2OFour・ 2H2O, H2C2OFourContent: 71.4% by weight) was dissolved in 4 l of water. Subsequently, 115.48 g of ammonium polyvanadate (V2OFiveContent: 88.2% by weight, ideal composition: (NHFour)2V6O16) Was dissolved by stirring, resulting in a dark blue aqueous solution (solution A). At that time, ammonium polyvanadate was added in small portions within 15 minutes to avoid bubbling of the reaction batch. 594.82 g ammonium heptamolybdate hydrate (MoOThreeContent: 81.3 wt%, ideal composition: (NHFour)6Mo7Otwenty four・ 4H2O) was dissolved by stirring in 4 l of warm water at 80 ° C. (solution B). Subsequently, at 80 ° C., solution B was continuously stirred into solution A within 15 minutes. The resulting dark blue aqueous solution was stirred at 80 ° C. for another 15 hours and then spray-dried (inlet temperature: 310 ° C., outlet temperature: 110 ° C.).
[0110]
100 g of the spray-dried powder was calcined in an air stream as described in MI7 at a rotational speed of 12 rpm in a horizontal rotary furnace with an isothermally heated quartz sphere capacity of 1 l.
[0111]
The resulting powdery multimetal oxide MI8 has a black color and a specific surface area of 5.3 m.2/ G (DIN 66131). Vanadium contained in the multimetal oxide MI8 is V4+As 52% and V5+As a percentage of 48%. At the same time, the multi-metal oxide MI8 is Mo.9.0V3.0O33.72Of stoichiometry. The visual phenomenon pattern of the associated Cu-Kα powder X-ray diffraction spectrum corresponds to the pattern of MI1 (see FIG. 16), and thus shows a spatial arrangement of atoms in common with MI1. Evaluation performed in the same manner as MI1 produced the following diffraction lines in the important 2θ range.
[0112]
[Table 21]
[Table 22]
MI9: Mo9.0V3.0O34.04
100 g of spray-dried powder produced for MI8 was calcined in an air stream as described in MI6 at a rotational speed of 12 rpm in a horizontal rotary furnace with an isothermally heated quartz sphere volume of 1 l. The resulting multi-metal oxide MI9 has a black color and a specific surface area of 5.7 m.2/ G (DIN 66131).
[0115]
Vanadium contained in the multimetal oxide MI9 is V4+As 31% and V5+As a proportion of 69%. Therefore, the multi-metal oxide MI9 is Mo9.0V3.0O34.04Of stoichiometry. The visual phenomenon pattern of the associated Cu-Kα powder X-ray diffraction spectrum corresponds to the MI1 pattern (see FIG. 17), and shows a spatial arrangement of atoms in common with MI1. Evaluation performed in the same manner as MI1 produced the following diffraction lines in the important 2θ range.
[0116]
[Table 23]
VMI2: Mo9.0V3.0O32.90
100 g of spray-dried powder produced with MI8 was calcined as described in MI1 in a horizontal rotary furnace with isothermally heated quartz sphere capacity of 1 l at a rotational speed of 12 rpm.
[0118]
The resulting multi-metal oxide VMI2 has a black color and a specific surface area of 6.8 m.2/ G (DIN 66131). Vanadium contained in the multimetal oxide VMI2 is V4+As 93% and V3+As a percentage of 7%. The visual phenomenon pattern of the associated Cu-Kα powder X-ray diffraction spectrum was clearly different from that of the multimetal oxide MI1 (see FIG. 18), and the following strong diffraction lines were produced in the 2θ range of 5 ° to 50 °.
[0119]
[Table 24]
2) Production of multimetal oxide II
MII1: German Patent 4440891 M5 starting material 1 (Cu12Mo12O48) Was post-processed.
[0121]
In 500 ml of water, 55.3 g of copper (II) oxide (CuO, Merck, Darmstadt, pure, at least 96%, powdered) and 100 g of molybdenum (VI) oxide (MoO)ThreeMerck, Darmstadt, degree of analysis, minimum 99.5%, powder). The entire aqueous dispersion was stirred (1000 rpm) in an autoclave (material, Hastelloy C4, internal volume: 2.5 l), heated to 350 ° C., stirred at this temperature and the associated overpressure and held for 24 hours. Subsequently, the autoclave was cooled to room temperature, the aqueous dispersion contained therein was taken out, the dispersed solid was filtered, and subsequently dried at 80 ° C. in a drying shelf. The resulting dry powder had crystal particles having a number average particle diameter of about 8 μm by scanning electron microscope analysis. A Cu / Mo ratio of about 1 was obtained by chemical analysis of the crystal grains.
[0122]
Using Cu-Kα radiation (Siemens-Diffraktometer D-5000, 40 kV, 30 mA, with automatic dispersion, scattering and counter collimator and Peltier detector), the crystalline powder CuMoOy shows the following X-ray diffraction pattern and used It is shown in the form of the relative intensities (%) of the various diffraction lines relative to the diffraction line of the highest intensity (width) associated with the lattice spacing d [Å] independent of the X-ray wavelength.
[0123]
[Table 25]
[Table 26]
[Table 27]
The display error of the lattice spacing d is ± 0.20 mm (low intensity lines probably include lines due to slight impurities), and this X-ray diffraction pattern is shown in the Russian Journal of Inorganic Chemistry 36 (7 ), 1991, page 927, CuMoO described in Table 1FourCorresponds to the pattern for -III.
[0127]
MII2: starting material 1 (Cu) of M3 of German Patent 1952864612Mo6W6O42 ~ 48) Was post-processed.
[0128]
223.05 g of ammonium heptamolybdate hydrate (MoOThreeContent: 81.3%, ideal composition: (NHFour)6Mo7Otwenty four・ 4H2O) and ammonium paratungstate hydrate 327.52 g (WOThreeContent: 89.2% by weight, ideal composition: (NHFour)TenW12O41・ 7H2O) was dissolved by stirring in 5 l of water at 90 ° C. (solution A). 492.64 g of copper acetate hydrate (Cu content: 32.5% by weight, ideal composition: Cu (CHThreeCOO)2・ H2O) 3 l of water and 197.88 g of 25% by weight aqueous ammonia solution were added and stirred for 15 minutes at 25 ° C., at which time a pale blue suspension was obtained (suspension B). Suspension B was subsequently stirred into solution A having 90 ° C., and the resulting suspension was stirred at 80 ° C. for a further 3 hours. The resulting aqueous suspension medium (Suspension C) had a pH value of 5.3 (glass electrode) after cooling to 25 ° C. Suspension C was spray dried at an inlet temperature of 310 ° C and an outlet temperature of 110 ° C.
[0129]
The green powder obtained is calcined in the air, continuously heated from 25 ° C. to 300 ° C. within 24 hours in the first stage, and continuously within 3 hours in the subsequent second stage. In the third stage, the temperature was maintained at 780 ° C. for 1 hour. Firing was carried out in a rotary furnace with a usable volume of 1 l, using 60 g of each starting spray powder and an air flow of 50 Nl / h.
[0130]
The resulting powder is brown and has a specific surface area of 0.3 m according to DIN 661312/ G and Cu12Mo6W6O42 ~ 48The composition was By scanning electron microscope analysis, the powder had crystal particles having a number average particle diameter of about 8 μm. Using Cu-Kα radiation (Siemens-Diffraktometer D-5000, 40 kV, 30 mA, with automatic dispersion, scattering and counter collimator and Peltier detector), the crystalline powder shows a powder X-ray graph, which is ferromanganese barite It showed an overlap between the fingerprint and the HT-copper molybdate fingerprint, ie it had a two-phase structure. Depending on the line strength, two structural types existed at a frequency ratio of about 60 (ferromanganese barite structure): 40 (HT-copper molybdate type).
[0131]
HT-copper molybdate structure type uses Cu-Kα radiation (with Siemens-Diffraktometer D-5000,48kV, 30mA, automatic dispersion, scattering and counter collimator and Peltier detector) according to the following X-ray diffraction graph CuMo0.9W0.1O3.5 ~ FourOf various diffractions (indicated by the attenuation intensity) for the diffraction line of the highest intensity (width) associated with the lattice spacing d [Å] independent of the wavelength of the X-ray used and represented by a crystalline powder of the composition It is shown in the form of the relative intensity (%) of the line.
[0132]
[Table 28]
[Table 29]
[Table 30]
The display error of the lattice spacing d is mainly ± 0.3 mm for d values of 2.9 mm or more, and ± 0.2 mm for d values smaller than 2.9 mm (low intensity line Includes a line probably due to slight impurities).
[0136]
3) Production of shell-type catalysts S1 to S3 and comparative shell-type catalysts SV1 to SV3
S1: 1) multimetal oxide MI1 (Mo8.54V2.47W0.99O33.53) To a particle diameter in the range of 0.1 to 50 μm, and the resulting active substance powder in a rotating drum is subjected to surface roughness Rz (
[0137]
SV1: carried out in the same way as S1, except that as active substance8.54V2.47W0.99O33.53A multi-metal oxide VMI1 prepared in 1) and having a composition of
[0138]
S2: Performed in the same manner as S1, but the active material produced in 1) was pulverized in a corresponding manner to the multimetal oxide MI1 (Mo12V3.47W1.39O47.11) And a centrifuge grinder, Retsch (Germany), and pulverized to a number average maximum particle diameter of 1 to 3 μm, MII1 (Cu12Mo12O48) Was used. MII1 was stirred into MI1 in such an amount that the molar ratio of the stoichiometric units in the resulting mixed powder was 6.5 (MI1): 1 (MII1). Mixing in an intensive mixer, Gustav Erich, Hardheim, Germany (type RO2, MPM apparatus) resulted in a complete mixture of the two powders. 600 g of the mixture was mixed in 15 minutes using a tank with a capacity of 10 l and a Stern impeller rotating at 900 rpm countercurrent to the tank and rotating at 64 rpm.
[0139]
The resulting biphasic active substance is:
[0140]
[Mo12V3.47W1.39O47.11]6.5[Cu12Mo12O48] ≒ Mo12VThreeW1.2Cu1.6O47.23
S3: Performed in the same manner as S2, except that the multimetal oxide MII2 prepared in 2) was used instead of the multimetal oxide MII1 prepared in 2).
[0141]
The resulting active substances are:
[0142]
[Mo12V3.47W1.39O47.11]6.5[Cu12Mo6W6O42 ~ 48]
SV2: Produced in the same manner as S1, except that finely dispersed powder produced as follows was used as the active substance.
[0143]
127 g of copper (II) acetate monohydrate (Cu 32.4% by weight) was dissolved in 2700 g of water to prepare Solution I. 860 g ammonium heptamolybdate tetrahydrate (MoOThree81.3% by weight), ammonium metavanadate 143 g (V2OFive77.2% by weight) and 126 g ammonium paratungstate heptahydrate (WOThree89.3% by weight) was sequentially dissolved in 5500 g of water at 95 ° C. to prepare Solution II. Subsequently, Solution I was immediately stirred into Solution II and the aqueous mixture heated to 80 ° C. was spray dried at an outlet temperature of 110 ° C.
[0144]
800 g of spray powder was kneaded and fired in the same manner as 800 g of spray powder for producing MI1. Thereafter, pulverization was performed to produce a particle diameter of 0.1 to 50 μm, and a shell-type catalyst similar to S1 was formed.
[0145]
Active substance stoichiometry: Mo12VThreeW1.2Cu1.6Ox *
FIG. 19 shows A in the range of 2θ = 5 ° to 50 °.1~ ATenTherefore, a Cu-Kα powder X-ray diffraction spectrum significantly different from the X-ray diffraction spectrum of the Cu-Kα powder of the multimetal oxide MI1 is exhibited.
[0146]
SV3: Same as SV2, except that only 3.6 Nl / h of air flowed through the firing furnace during the entire firing time.
[0147]
Active substance stoichiometry: Mo12VThreeW1.2Cu1.6Ox **
4). Use of the shell-type catalyst produced in 3) as a catalyst for gas phase oxidation to produce acrylic acid from acrolein
The catalyst was introduced into a tubular reactor (V2A stainless steel,
Acrolein 5% by volume,
7% oxygen by volume,
10% by volume of steam and
Nitrogen 78% by volume
A gaseous mixture consisting of was fed at a reaction temperature of 250-270 ° C. using a residence time of 2.0 seconds. In all cases, the salt bath temperature was adjusted to give a uniform acrolein conversion of 99% after one pass after molding. The product gas mixture produced in the reactor was analyzed by gas chromatography. The selectivity results for acrylic acid formation using various catalysts are shown in the table below.
[0148]
[Table 31]
The conversion rate, selectivity and remaining time are shown below.
[0150]
Acrolein conversion C (%) = (moles of acrolein converted / moles of acrolein charged) × 100
Selectivity of acrylic acid formation S (%) = (number of moles of acrolein converted to acrylic acid / number of moles of all converted acrolein) × 100
Residence time (seconds) = (space capacity of reactor filled with catalyst (l) / amount of synthesis gas charged (Nl / h)) × 3600
[Brief description of the drawings]
FIG. 1 is a CuKα powder X-ray diffraction spectrum showing the spatial arrangement of a multimetal oxide MI1.
FIG. 2 is an enlarged view of the 2θ range of 5 to 43 ° of the spectrum.
FIG. 3 is an enlarged view of a 2θ range of 43 to 65 ° of the spectrum.
FIG. 4 is a CuKα powder X-ray diffraction spectrum showing the spatial arrangement of the multimetal oxide MI3.
FIG. 5 is an enlarged view of the 2θ range of 5 to 43 ° of the spectrum.
FIG. 6 is an enlarged view of the 2θ range of 43 to 65 ° of the spectrum.
FIG. 7 is a CuKα powder X-ray diffraction spectrum showing the spatial arrangement of a multimetal oxide MI4.
FIG. 8 is an enlarged view of a 2θ range of 5 to 43 ° of the spectrum.
FIG. 9 is an enlarged view of the 2θ range of 43 to 65 ° of the spectrum.
FIG. 10 is a CuKα powder X-ray diffraction spectrum showing the spatial arrangement of a multimetal oxide MI5.
FIG. 11 is an enlarged view of the 2θ range of 5 to 43 ° of the spectrum.
FIG. 12 is an enlarged view of the 2θ range of 43 to 65 ° of the spectrum.
FIG. 13 is a CuKα powder X-ray diffraction spectrum showing the spatial arrangement of a comparative multimetal oxide VMI1.
FIG. 14 is a CuKα powder X-ray diffraction spectrum showing the spatial arrangement of a multimetal oxide MI6.
FIG. 15 is a view of a CuKα powder X-ray diffraction spectrum showing a spatial arrangement of a multimetal oxide MI7.
FIG. 16 is a CuKα powder X-ray diffraction spectrum showing the spatial arrangement of a multimetal oxide MI8.
FIG. 17 is a view of a CuKα powder X-ray diffraction spectrum showing a spatial arrangement of a multimetal oxide MI9.
FIG. 18 is a CuKα powder X-ray diffraction spectrum showing the spatial arrangement of a comparative multimetal oxide VMI2.
FIG. 19 is a CuKα powder X-ray diffraction spectrum showing the spatial arrangement of the manufactured shell-type catalyst.
Claims (11)
Ｍｏ12-a-b-cＶaＭ1 bＭ2 cＯx （Ｉ）
［式中、
Ｍ1＝Ｗ、
Ｍ2＝Ｔｉ，Ｚｒ，Ｈｆ，Ｔａ，Ｃｒ，Ｓｉ及び／又はＧｅ、
ａ＝０．１〜６、
ｂ＝０〜６、
ｃ＝０
であり、但しａ＋ｂ＋ｃ＝０．１〜６であり、かつ
ｘ＝式Ｉ中の酸素とは異なる元素の原子価及び頻度により決まる数値
である］の多金属酸化物からなるアクロレインからアクリル酸への接触気相酸化用触媒において、該多金属酸化物の、Ｃｕ-Ｋα放射線（λ＝１．５４１７８Å）を使用して得られた三次元的原子配置が、５〜５０゜の２θ範囲内で少なくとも以下の特性回折線Ａ1，Ａ3，Ａ5，Ａ9及びＡ10、但し最大でも以下の回折線Ａ1〜Ａ10を含む、Ｘ線粉末回折スペクトル（２倍の回折角度（２θ）の関数としてプロットした回折したＸ線の強度Ａ）：
Mo 12-abc V a M 1 b M 2 c O x (I)
[Where:
M 1 = W
M 2 = Ti, Zr, Hf, Ta, Cr, Si and / or Ge,
a = 0.1-6,
b = 0 to 6,
c = 0
Wherein a + b + c = 0.1-6, and x = a value determined by the valence and frequency of an element different from oxygen in Formula I] . In the catalyst for catalytic gas phase oxidation, the three-dimensional atomic arrangement of the polymetal oxide obtained using Cu-Kα radiation (λ = 1.54178Å) is at least within a 2θ range of 5 to 50 °. The following characteristic diffraction lines A 1 , A 3 , A 5 , A 9 and A 10 , but including at most the following diffraction lines A 1 to A 10 , an X-ray powder diffraction spectrum (double diffraction angle (2θ)) Intensity of diffracted X-rays plotted as a function A):
Ｍｏ12-a-b-cＶaＭ1 bＭ2 cＯx （Ｉ）
［式中、
Ｍ1＝Ｗ、
Ｍ2＝Ｔｉ，Ｚｒ，Ｈｆ，Ｔａ，Ｃｒ，Ｓｉ又はＧｅ、
ａ＝０．１〜６、
ｂ＝０〜６、
ｃ＝０
であり、但しａ＋ｂ＋ｃ＝０．１〜６であり、かつ
ｘ＝式Ｉ中の酸素は異なる元素の原子価及び頻度により決まる数値
である］の多金属酸化物からなるアクロレインからアクリル酸への接触気相酸化用触媒において、該多金属酸化物の三次元的原子配置が、以下のようにして得られた多金属酸化物Ｍｏ8.54Ｖ2.47Ｗ0.99Ｏ33.35に相当する：
ヘプタモリブデン酸アンモニウム水和物（ＭｏＯ3含量：８１．８重量％、理想組成：（ＮＨ4）6Ｍｏ7Ｏ24×４Ｈ2Ｏ）３３．７４６ｋｇ、メタバナジウム酸アンモニウム（Ｖ2Ｏ5含量：７６．５重量％、理想組成：ＮＨ4ＶＯ3）６．５７６ｋｇ、パラタングステン酸アンモニウム水和物（ＷＯ3含量：８９．０重量％、理想組成： （ＮＨ4）10Ｗ12Ｏ41×７Ｈ2Ｏ）５．７６４ｋｇ及び酢酸アンモニウム（ＣＨ3ＣＯＯＮＨ4含量：９７．０重量％、理想組成：ＣＨ3ＣＯＯＮＨ4）７．０３３ｋｇを、前記順序で順次に９０℃の温度で水２５０ ｌ中に撹拌下に溶かし、生じた黄〜オレンジ色の溶液を８０℃に冷却しかつ３００℃の入口温度及び１１０℃の出口温度で噴霧乾燥し；
得られた噴霧粉末８００ｇを、２．５ ｌの有効容積を有するニーダ（Fa. Werner und Pfleiderer, 7000 Stuttgart, DEのTyp LUK）内で水２５０ｇを加えて１ｈ混練し、その際水２５０ｇのうちの１８０ｇは初めの１０分間以内でニーダに加えかつ７０ｇは残りの５０分間以内で加え、生じる湿った塊状の混練生成物を１１０℃の温度で１５ｈ乾燥させかつその後５ｍｍのメッシュ幅を有するふるいを通して押出し；
その際生じるグラニュール１００ｇを、引き続き１ ｌの等温加熱される石英球体積及び１２ｒｐｍの回転速度を有する回転炉内で焼成する、その際焼成条件は以下のように構成する：
第１段階：装入したグラニュールを５０分間以内で連続的に２５℃から２７５℃に加熱する；
第２段階：装入したグラニュールを３０分間以内で連続的に２７５℃から３２５℃に加熱する；
第３段階：装入したグラニュールを３２５℃で４時間保持する；
第４段階：装入したグラニュールを３０分間以内で連続的に３２５℃から４００℃に加熱する；
第５段階：装入したグラニュールを４００℃で１０分間保持する；
引き続き回転炉の外部加熱装置のスイッチを切り、回転炉を周囲空気を外部から吹き付けることにより冷却し、その際装入したグラニュールを５時間以内で２５℃に冷却し；
個々の焼成段階中に、回転炉の内部に回転軸に対して平行に、以下の組成（標準条件（Ｎ）＝１ａｔｍ、２５℃）：
第１段階、第２段階及び第３段階：空気３．６Ｎｌ／ｈ、ＮＨ3 １．５Ｎｌ／ｈ及びＮ2 ４４．９Ｎｌ／ｈ（全ガス流量：５０Ｎｌ／ｈ）；
第４段階、第５段階及び冷却期間：空気３．６Ｎｌ／ｈ及びＮ2 ４４．９Ｎｌ／ｈ（全ガス流量：４８．５Ｎｌ／ｈ）
を有するガス混合物を貫流させる
ことを特徴とする、請求項１から３までのいずれかに記載の、アクロレインからアクリル酸への接触気相酸化用触媒。Formula I:
Mo 12-abc V a M 1 b M 2 c O x (I)
[Where:
M 1 = W
M 2 = Ti, Zr, Hf, Ta, Cr, Si or Ge,
a = 0.1-6,
b = 0 to 6,
c = 0
Where a + b + c = 0.1-6, and x = oxygen in formula I is a value determined by the valence and frequency of different elements] from acrolein consisting of a multimetallic oxide to acrylic acid In the gas phase oxidation catalyst , the three-dimensional atomic arrangement of the multimetal oxide corresponds to the multimetal oxide Mo 8.54 V 2.47 W 0.99 O 33.35 obtained as follows:
Heptamolybdate hydrate (MoO 3 content: 81.8% by weight, ideal composition: (NH 4 ) 6 Mo 7 O 24 × 4H 2 O) 33.746 kg, ammonium metavanadate (V 2 O 5 content: 76.5% by weight, ideal composition: NH 4 VO 3 ) 6.576 kg, ammonium paratungstate hydrate (WO 3 content: 89.0% by weight, ideal composition: (NH 4 ) 10 W 12 O 41 × 7H 2 O) 5.764 kg and ammonium acetate (CH 3 COONH 4 content: 97.0% by weight, ideal composition: CH 3 COONH 4 ) in the order of 9033 ° C. in 250 liters of water at the temperature of 90 ° C. Dissolved under stirring, the resulting yellow-orange solution is cooled to 80 ° C. and spray dried at an inlet temperature of 300 ° C. and an outlet temperature of 110 ° C .;
800 g of the resulting spray powder was kneaded for 1 h in a kneader (Typ LUK of Fa. Werner und Pfleiderer, 7000 Stuttgart, DE) having an effective volume of 2.5 l, with 250 g of water being mixed. 180 g of is added to the kneader within the first 10 minutes and 70 g is added within the remaining 50 minutes, and the resulting wet mass kneaded product is dried at a temperature of 110 ° C. for 15 h and then passed through a sieve having a mesh width of 5 mm. Extrusion;
The resulting granule 100 g is subsequently fired in a rotary furnace having a 1 l isothermally heated quartz sphere volume and a rotational speed of 12 rpm, the firing conditions being configured as follows:
1st stage: The charged granules are continuously heated from 25 ° C. to 275 ° C. within 50 minutes;
Second stage: the charged granules are continuously heated from 275 ° C. to 325 ° C. within 30 minutes;
Third stage: hold the charged granules at 325 ° C. for 4 hours;
4th stage: The charged granules are continuously heated from 325 ° C. to 400 ° C. within 30 minutes;
Stage 5: Hold the charged granules at 400 ° C. for 10 minutes;
Subsequently switch off the external heating device for a rotary furnace, and cooled by blowing rotary furnace ambient air from the outside, cooling the SaiSoIri the granules to 25 ° C. within 5 hours;
During the individual firing steps, the following composition (standard conditions (N) = 1 atm, 25 ° C.) parallel to the axis of rotation inside the rotary furnace:
First, second and third stages: air 3.6 Nl / h, NH 3 1.5 Nl / h and N 2 44.9 Nl / h (total gas flow: 50 Nl / h);
4th stage, 5th stage and cooling period: air 3.6 Nl / h and N 2 44.9 Nl / h (total gas flow rate: 48.5 Nl / h)
A catalyst for catalytic gas phase oxidation of acrolein to acrylic acid according to any one of claims 1 to 3, characterized in that a gas mixture comprising
Ｍ3 12ＣｕdＨeＯy （ＩＩ）
［式中、
Ｍ3＝Ｍｏ，Ｗ，Ｖ，Ｎｂ又はＴａ、
ｄ＝４〜３０、
ｅ＝０〜２０及び
ｙ＝式ＩＩ中の酸素とは異なる元素の原子価及び頻度により決まる数値
である］の微細多金属酸化物を含有する微細物質混合物からなるアクロレインからアクリル酸への接触気相酸化用触媒。Fine multi-metal oxides of general formula (I) as defined in any of claims 1 to 4 and general formula II:
M 3 12 Cu d H e O y (II)
[Where:
M 3 = Mo, W, V, Nb or Ta,
d = 4-30,
e = 0 to 20 and y = a numerical value determined by the valence and frequency of an element different from oxygen in formula II] . The contact gas from acrolein to acrylic acid comprising a fine substance mixture containing a fine multimetal oxide Phase oxidation catalyst .
［Ａ］p［Ｂ］q （III）
［式中、
Ｍ1＝Ｗ、
Ｍ2＝Ｔｉ，Ｚｒ，Ｈｆ，Ｔａ，Ｃｒ，Ｓｉ又はＧｅ、
ａ＝０．１〜６、
ｂ＝０〜６、
ｃ＝０
であり、但しａ＋ｂ＋ｃ＝０．１〜６であり、
ｘ＝Ａ中の酸素とは異なる元素の原子価及び頻度により決まる数値、
Ｍ3＝Ｍｏ，Ｗ，Ｖ，Ｎｂ又はＴａ、
ｄ＝４〜３０、
ｅ＝０〜２０、
ｙ＝Ｂ中の酸素とは異なる元素の原子価及び頻度により決まる数値、
ｐ，ｑ＝０とは異なる数値、その比ｐ／ｑは１６０：１〜１：１である］を有し、
成分［Ａ］pを三次元的に拡がり、その局所的周囲からその局所的周囲とは異なる化学的組成に基づき境界付けられる化学組成：
Ａ Ｍｏ12-a-b-cＶaＭ1 bＭ2 cＯx
の領域Ａの形で、かつ
成分［Ｂ］qを三次元的に拡がり、その局所的周囲からその局所的周囲とは異なる化学的組成に基づき境界付けられる化学組成：
Ｂ Ｍ3 12ＣｕdＨeＯy
の領域Ｂの形で含有し、その際、領域Ａ，Ｂは互いに相対的に微粒子状Ａと微粒子状Ｂからなる混合物におけるように分配されており、かつ領域Ａの、Ｃｕ-Ｋα放射線（λ＝１．５４１７８Å）を使用して得られた三次元的原子配置が、５〜５０゜の２θ範囲内で少なくとも以下の特性回折線Ａ1，Ａ3，Ａ5，Ａ9及びＡ10、但し最大でも以下の回折線Ａ1〜Ａ10を含む、Ｘ線粉末回折スペクトル（２倍の回折角度（２θ）の関数としてプロットした回折したＸ線の強度）：
[A] p [B] q (III)
[Where:
M 1 = W
M 2 = Ti, Zr, Hf, Ta, Cr, Si or Ge,
a = 0.1-6,
b = 0 to 6,
c = 0
Where a + b + c = 0.1-6,
x = a numerical value determined by the valence and frequency of an element different from oxygen in A,
M 3 = Mo, W, V, Nb or Ta,
d = 4-30,
e = 0 to 20,
y = a numerical value determined by the valence and frequency of an element different from oxygen in B,
p, q = 0, a different numerical value, the ratio p / q is 160: 1 to 1: 1]
Chemical composition that extends component [A] p three-dimensionally and is bounded from its local surroundings based on a different chemical composition from its local surroundings:
A Mo 12-abc V a M 1 b M 2 c O x
In the form of areas A, and component [B] q spread in three-dimensional, chemical composition bounded on the basis of different chemical composition and their local surroundings from its local surroundings:
B M 3 12 Cu d H e O y
In this case, the regions A and B are distributed relative to each other as in the mixture of the fine particles A and the fine particles B, and the Cu-Kα radiation (λ = 1.54178 Å), the three-dimensional atomic arrangement obtained at least within the 2θ range of 5 to 50 ° is the following characteristic diffraction lines A 1 , A 3 , A 5 , A 9 and A 10 , X-ray powder diffraction spectrum (diffracted X-ray intensity plotted as a function of double diffraction angle (2θ)), including at most the following diffraction lines A 1 -A 10 :
［Ａ］p［Ｂ］q （III）
［式中、
Ｍ1＝Ｗ、
Ｍ2＝Ｔｉ，Ｚｒ，Ｈｆ，Ｔａ，Ｃｒ，Ｓｉ又はＧｅ、
ａ＝０．１〜６、
ｂ＝０〜６、
ｃ＝０
であり、但しａ＋ｂ＋ｃ＝０．１〜６であり、
ｘ＝Ａ中の酸素とは異なる元素の原子価及び頻度により決まる数値、
Ｍ3＝Ｍｏ，Ｗ，Ｖ，Ｎｂ又はＴａ、
ｄ＝４〜３０、
ｅ＝０〜２０、
ｙ＝Ｂ中の酸素とは異なる元素の原子価及び頻度により決まる数値、
ｐ，ｑ＝０とは異なる数値、その比ｐ／ｑは１６０：１〜１：１である］を有し、
成分［Ａ］pを三次元的に拡がり、その局所的周囲からその局所的周囲とは異なる化学的組成に基づき境界付けられる化学組成：
Ａ Ｍｏ12-a-b-cＶaＭ1 bＭ2 cＯx
の領域Ａの形で、かつ
成分［Ｂ］qを三次元的に拡がり、その局所的周囲からその局所的周囲とは異なる化学的組成に基づき境界付けられる化学組成：
Ｂ Ｍ3 12ＣｕdＨeＯy
の領域Ｂの形で含有し、その際、領域Ａ，Ｂは互いに相対的に微粒子状Ａと微粒子状Ｂからなる混合物におけるように分配されており、かつ領域Ａの三次元的原子配置が、請求項４記載の多金属酸化物の三次元的原子配置である、少なくとも２相の多金属酸化物材料からなるアクロレインからアクリル酸への接触気相酸化用触媒。Formula III:
[A] p [B] q (III)
[Where:
M 1 = W
M 2 = Ti, Zr, Hf, Ta, Cr, Si or Ge,
a = 0.1-6,
b = 0 to 6,
c = 0
Where a + b + c = 0.1-6,
x = a numerical value determined by the valence and frequency of an element different from oxygen in A,
M 3 = Mo, W, V, Nb or Ta,
d = 4-30,
e = 0 to 20,
y = a numerical value determined by the valence and frequency of an element different from oxygen in B,
p, q = 0, a different numerical value, the ratio p / q is 160: 1 to 1: 1]
Chemical composition that extends component [A] p three-dimensionally and is bounded from its local surroundings based on a different chemical composition from its local surroundings:
A Mo 12-abc V a M 1 b M 2 c O x
In the form of areas A, and component [B] q spread in three-dimensional, chemical composition bounded on the basis of different chemical composition and their local surroundings from its local surroundings:
B M 3 12 Cu d H e O y
In this case, the regions A and B are distributed relative to each other as in the mixture of the particulate A and the particulate B, and the three-dimensional atomic arrangement of the region A is A catalyst for catalytic gas phase oxidation of acrolein to acrylic acid, comprising a multimetal oxide material of at least two phases, which is a three-dimensional atomic arrangement of the multimetal oxide according to claim 4.
Ｍ3 12ＣｕdＨeＯy （ＩＩ）
［式中、
Ｍ3＝Ｍｏ，Ｗ，Ｖ，Ｎｂ又はＴａ、
ｄ＝４〜３０、
ｅ＝０〜２０及び
ｙ＝式ＩＩ中の酸素とは異なる元素の原子価及び頻度により決まる数値
である］の微細な多金属酸化物を含有する微細物質混合物とをそれぞれ別々に前形成し、別々に前形成した微細な多金属酸化物ＩとＩＩとを混合して完全乾燥混合物とし、かつ完全乾燥混合物を成形することを特徴とする、アクロレインからアクリル酸を製造するための触媒の製造方法。The method for producing a catalytic gas phase oxidation catalyst from acrolein to acrylic acid comprising the multi-metal oxide material of the general formula (III) according to claim 7 as an active material, according to any one of claims 1 to 4. At least one fine multimetal oxide of the general formula (I)
M 3 12 Cu d H e O y (II)
[Where:
M 3 = Mo, W, V, Nb or Ta,
d = 4-30,
e = 0 to 20 and y = a numerical value determined by the valence and frequency of an element different from oxygen in Formula II], and each separately forming a fine material mixture containing a fine multimetallic oxide, A process for producing a catalyst for the production of acrylic acid from acrolein, characterized in that it separately mixes the pre-formed fine multimetal oxides I and II into a completely dry mixture and forms the completely dry mixture .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19542755A DE19542755A1 (en) | 1995-11-16 | 1995-11-16 | Multimetal oxides |
| DE19542755.6 | 1995-11-16 |
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| Publication Number | Publication Date |
|---|---|
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| JP (1) | JP4068679B2 (en) |
| KR (1) | KR970025702A (en) |
| CN (2) | CN1081486C (en) |
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| JP7186295B2 (en) * | 2019-06-05 | 2022-12-08 | 株式会社日本触媒 | Catalyst for producing acrylic acid, method for producing the same, and method for producing acrylic acid |
| EP4349787A1 (en) | 2021-05-25 | 2024-04-10 | Toshiba Materials Co., Ltd. | Multicomponent system complex oxide powder, electrochemical device and catalyst using same, and multicomponent system complex oxide powder production method |
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| US3147084A (en) | 1962-03-08 | 1964-09-01 | Shell Oil Co | Tubular catalytic reactor with cooler |
| BE793928A (en) | 1972-01-13 | 1973-05-02 | Deggendorfer Werft Eisenbau | APPARATUS FOR IMPLEMENTING EXOTHERMAL AND ENDOTHERMAL CHEMICAL PROCESSES |
| IT1001977B (en) * | 1973-11-28 | 1976-04-30 | Sir Soc Italiana Resine Spa | PROCEDURE FOR THE PREPARATION OF METHYL ACRYLATE OR MIXTURES OF METHYL ACRYLATE AND ACRILIC ACID |
| US4035262A (en) | 1976-04-19 | 1977-07-12 | The Dow Chemical Company | Acrolein oxidation catalyst |
| US4208306A (en) * | 1976-04-19 | 1980-06-17 | The Dow Chemical Company | Catalyst for making acrylic acid from acrolein or propylene |
| AU529228B2 (en) | 1977-07-13 | 1983-06-02 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Catalytic vapour phase oxidation |
| US4148757A (en) | 1977-08-10 | 1979-04-10 | The Standard Oil Company | Process for forming multi-component oxide complex catalysts |
| DE2909671A1 (en) | 1979-03-12 | 1980-10-02 | Basf Ag | METHOD FOR PRODUCING SHELL CATALYSTS |
| US4537874A (en) | 1982-10-22 | 1985-08-27 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for production of unsaturated aldehydes |
| DE3867912D1 (en) * | 1987-06-05 | 1992-03-05 | Nippon Catalytic Chem Ind | CATALYST FOR THE OXYDING OF ACROLEIN AND METHOD FOR THE PRODUCTION THEREOF. |
| US5270277A (en) * | 1990-08-08 | 1993-12-14 | Siemens Aktiengesellschaft | Arsenic-resistant catalyst and method for producing the same |
| DE4220859A1 (en) | 1992-06-25 | 1994-01-05 | Basf Ag | Multimetal oxide materials |
| DE4302991A1 (en) * | 1993-02-03 | 1994-08-04 | Basf Ag | Multimetal oxide materials |
| US5390448A (en) | 1993-04-22 | 1995-02-21 | Sunnen Products Company | Modular expandable honing tool |
| DE4335973A1 (en) | 1993-10-21 | 1995-04-27 | Basf Ag | Process for the preparation of catalytically active multimetal oxide compositions containing as basic constituents the elements V and Mo in oxidic form |
| DE4405060A1 (en) | 1994-02-17 | 1995-08-24 | Basf Ag | Multimetal oxide materials |
| DE4405059A1 (en) | 1994-02-17 | 1995-08-24 | Basf Ag | Multimetal oxide materials |
| DE4405058A1 (en) * | 1994-02-17 | 1995-08-24 | Basf Ag | Multimetal oxide materials |
| DE4405514A1 (en) | 1994-02-22 | 1995-08-24 | Basf Ag | Multi:metal oxide useful as catalyst esp. in gas phase oxidn. of acrolein to acrylic acid |
| DE4440891A1 (en) | 1994-11-17 | 1996-05-23 | Basf Ag | Multi:metal oxide useful as catalyst esp. in gas phase oxidn. of acrolein to acrylic acid |
| JP3786297B2 (en) * | 1995-03-03 | 2006-06-14 | 日本化薬株式会社 | Catalyst production method |
| DE19528646A1 (en) * | 1995-08-04 | 1997-02-06 | Basf Ag | multimetal |
| DE19542755A1 (en) * | 1995-11-16 | 1997-05-22 | Basf Ag | Multimetal oxides |
-
1995
- 1995-11-16 DE DE19542755A patent/DE19542755A1/en not_active Withdrawn
-
1996
- 1996-11-05 US US08/744,246 patent/US5807531A/en not_active Expired - Fee Related
- 1996-11-07 DE DE59604408T patent/DE59604408D1/en not_active Expired - Fee Related
- 1996-11-07 ES ES96117834T patent/ES2143702T3/en not_active Expired - Lifetime
- 1996-11-07 EP EP96117834A patent/EP0774297B1/en not_active Expired - Lifetime
- 1996-11-12 CA CA002190171A patent/CA2190171A1/en not_active Abandoned
- 1996-11-14 MX MX9605566A patent/MX9605566A/en not_active Application Discontinuation
- 1996-11-14 SG SG1996011112A patent/SG69990A1/en unknown
- 1996-11-15 CN CN96114492A patent/CN1081486C/en not_active Expired - Fee Related
- 1996-11-15 ID IDP963350A patent/ID16006A/en unknown
- 1996-11-15 CN CNB011244747A patent/CN1177763C/en not_active Expired - Fee Related
- 1996-11-15 MY MYPI96004750A patent/MY132599A/en unknown
- 1996-11-15 KR KR1019960054200A patent/KR970025702A/en not_active Application Discontinuation
- 1996-11-15 CZ CZ963362A patent/CZ336296A3/en unknown
- 1996-11-18 JP JP30644296A patent/JP4068679B2/en not_active Expired - Fee Related
-
1998
- 1998-06-05 US US09/092,181 patent/US6084126A/en not_active Expired - Fee Related
-
2000
- 2000-01-27 US US09/492,226 patent/US6184173B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0774297B1 (en) | 2000-02-09 |
| KR970025702A (en) | 1997-06-24 |
| CA2190171A1 (en) | 1997-05-17 |
| CN1153079A (en) | 1997-07-02 |
| CN1177763C (en) | 2004-12-01 |
| ES2143702T3 (en) | 2000-05-16 |
| JPH09194213A (en) | 1997-07-29 |
| US6084126A (en) | 2000-07-04 |
| US5807531A (en) | 1998-09-15 |
| CZ336296A3 (en) | 1997-08-13 |
| MX9605566A (en) | 1997-05-31 |
| SG69990A1 (en) | 2000-01-25 |
| MY132599A (en) | 2007-10-31 |
| EP0774297A1 (en) | 1997-05-21 |
| DE19542755A1 (en) | 1997-05-22 |
| DE59604408D1 (en) | 2000-03-16 |
| CN1081486C (en) | 2002-03-27 |
| US6184173B1 (en) | 2001-02-06 |
| CN1394812A (en) | 2003-02-05 |
| ID16006A (en) | 1997-08-28 |
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